JPH06308750A - Optical sensor and information recording system - Google Patents

Abstract

PURPOSE:To provide an optical sensor having a large amplification function and the information recording system. CONSTITUTION:The optical sensor having the chemical constitutional formula of formula is used as the optical sensor for the information recording system which is arranged with the optical sensor constituted by providing a base material with an electrode layer thereon and laminating a photoconductive layer on this electrode layer and an information recording medium constituted by laminating an information recording layer capable of recording information by electric fields or electric charges on the electrode layer in opposition to each other and enables recording of information on the information recording medium by information exposing in the state of impressing a voltage between both electrodes. In the formula, A and B denote the same or different alkyl group, alalkyl group, cycloalkyl group, carbon cyclic or heterocyclic arom. group; R1, R2 denote a hydrogen atom or substituent which does not impart water solubility. As a result, the optical sensor having the large amplification factor and the information recording system are obtd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an information recording system comprising an optical sensor capable of recording optical information in the form of visible information or electrostatic information on an information recording medium and an information recording medium, and further to an information recording method. In particular, the present invention relates to an optical sensor and an information recording system in which information recording performance on an information recording medium is remarkably amplified.

[0002]

2. Description of the Related Art An optical sensor comprising a photoconductive layer having an electrode layer on the front surface and an information recording medium comprising a charge holding layer having an electrode layer provided on the rear surface facing the optical sensor are arranged on the optical axis. And expose while applying voltage between both conductive layers,
A method of recording an electrostatic charge on a charge holding layer according to an incident optical image and reproducing the electrostatic charge by toner development or potential reading is disclosed in, for example, JP-A-1-29036.
No. 6 and Japanese Patent Laid-Open No. 1-289975. Further, the charge retention layer in the above method is a thermoplastic resin layer, electrostatic charges are recorded on the surface of the thermoplastic resin layer and then heated to form a frost image on the surface of the thermoplastic resin layer, thereby recording the electrostatic charge. The method of visualizing the is described in, for example, Japanese Patent Laid-Open No. 3-192288.

Furthermore, the applicant of the present invention, the information recording layer in the above information recording medium is a polymer dispersion type liquid crystal layer, and is exposed under voltage application similarly to the above, and the liquid crystal layer is aligned by an electric field formed by a photosensor. Information recording / reproducing method in which information recording is performed by reproducing information as visible information by transmitting light or reflected light when reproducing information recording (Japanese Patent Application Nos. 2-186023 and 3-10847) did. This information recording / reproducing method makes it possible to visualize recorded information without using a deflector.

[0004]

SUMMARY OF THE INVENTION The present invention is an optical sensor used for forming information on an information recording medium as described above, which is excellent in information forming ability and has improved information recording sensitivity and information recording. The challenge is to provide a system.

[0005]

The optical sensor of the present invention comprises:
An optical sensor in which an electrode layer is provided on a base material and a photoconductive layer is laminated on the electrode layer, and an information recording medium in which an information recording layer capable of recording information by an electric field or electric charge is laminated on the electrode layer. And the photoconductive layer of the photosensor used in the information recording system which is arranged so as to face each other and enables the information recording on the information recording medium by the information exposure in the state where the voltage is applied between the two electrode layers. It is an optical sensor containing the pyrrolopyrrole compound represented by 1).

[0006]

[Chemical 3]

In the above chemical structural formulas, A and B
Represent the same or different alkyl groups, aralkyl groups, cycloalkyl groups, carbocyclic or heterocyclic aromatic groups, and R ₁ and R ₂ represent hydrogen atoms or substituents which do not impart water solubility. In addition, an optical sensor has an electrode layer and a photoconductive layer laminated on a base material, and the electric field strength or the amount of electric charge applied to the information recording medium is amplified as the light is irradiated, and a voltage is applied even after the light irradiation is completed. It is an optical sensor that has the effect of continuing its conductivity when continuously kept on, and then continuously applying the electric field strength or the amount of charge to the information recording medium. Also,
An optical sensor having a photoconductive layer containing a pyrrolopyrrole compound represented by the above chemical structural formula on an electrode layer formed on a substrate, and an information recording layer capable of recording information by an electric field or electric charge on the electrode layer. This is an information recording system which is arranged so as to face a laminated information recording medium and enables information recording on the information recording medium by information exposure in a state where a voltage is applied between both electrodes.

The present invention will be described in detail below. First, in the photosensor of the present invention, a photoconductive layer is laminated on an electrode layer, and a charge generation layer and a charge transport layer are laminated on the photoconductive layer. The photoconductive layer generally has a function of generating photocarriers (electrons and holes) in the irradiated portion when irradiated with light, and these carriers can move in the layer width. Although the effect is significant when present, the photosensor of the present invention is an information recording medium at the time of light irradiation to the photosensor by appropriately combining a photoconductive layer and an electrode layer described below. The applied electric field or the amount of electric charge is amplified as the light is irradiated, and even after the light irradiation is finished, the conductivity is maintained when the voltage is continuously applied,
The function of continuously applying the electric field strength or the charge amount to the information recording medium is obtained.

FIG. 1 is a sectional view for explaining an optical sensor of the present invention, showing an optical sensor 1 in which a photoconductive layer is composed of two layers, a charge generation layer and a charge transport layer. The optical sensor has the charge generation layer 1 on the electrode layer 13 formed on the substrate 15.
4'and a charge transport layer 14 '' are formed. The charge generation layer 14 'forming the photoconductive layer of the photosensor of the present invention is a pyrrolopyrrole compound represented by the following chemical structural formula. Contains.

[0010]

[Chemical 4]

In the above chemical formula, A and B
Represent the same or different alkyl groups, aralkyl groups, cycloalkyl groups, carbocyclic or heterocyclic aromatic groups, and R ₁ and R ₂ represent hydrogen atoms or substituents which do not impart water solubility. A and B are compounds having the same or different groups represented by the following formula (2).

[0012]

[Chemical 5]

In the above formula (2), the substituents X, Y and Z are hydrogen atom, halogen atom, trifluoromethyl group, cyano group, alkyl group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms. Alkoxy group having 1 to 12 carbon atoms
, An alkylmercapto group, an alkoxycarbonyl group having 2 to 4 carbon atoms, a dialkylamino group having 2 to 6 carbon atoms, or an unsubstituted or halogen atom, an alkyl group having 1 to 6 carbon atoms or 1 to carbon atoms, respectively. A phenoxy group, a phenylmercapto group or a phenoxycarbonyl group substituted by an alkoxy group of 6, wherein the substituents X, Y and Z may be different or the same, X
And at least one of Z represents a hydrogen atom.

In the formula (1), A and B as an alkyl group may be linear or branched, saturated or unsaturated, preferably 1-18, more preferably 1-12. Containing a carbon atom, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, secondary butyl group, tertiary butyl group, tertiary amyl group, n-pentyl group, n-hexyl group, 1,1,3,3
-Tetramethylbutyl group, n-heptyl group, n-octyl group, nonyl group, decyl group, undecyl group, dodecyl group or stearyl group.

A and B as the aralkyl group preferably have 1 to 12 carbon atoms having a straight or branched chain, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms. It includes a monocyclic to tricyclic aryl group having an alkenyl group, and most preferably a monocyclic or bicyclic aryl group. Examples of such aralkyl groups include benzyl and phenylethyl groups. A and B as aromatic groups are preferably monocyclic or tetracyclic groups, more preferably monocyclic or bicyclic groups such as phenyl group, diphenyl group or naphthyl group. . A and B as the heterocyclic aromatic group are preferably monocyclic or tricyclic groups. These groups can be pure heterocyclic groups or those containing one or more fused benzene rings with a heterocyclic group, for example pyridyl, pyrimidyl, pyrazinyl, triazinyl, furanyl. Group, pyrrolyl group, thiophenyl group, quinolyl group, coumarinyl group, benzofuranyl group, benzimidazolyl group, benzoxazolyl group, dibenzofuranyl group, benzothiophenyl group, indolyl group, carbazolyl group, pyrazolyl group, imidazolyl group, oxazole Base,
Isoxazol group, thiazolyl group, indazolyl group, benzothiazolyl group, pyridazodinyl group, cinnolyl group,
Quinazolyl group, quinoxalyl group, phthalazinyl group, phthalazine dionyl group, phthalimidyl group, chromonyl group,
Naphtholactamyl group, benzopyridonyl group, maleimidyl group, naphthalidinyl group, benzimidazolonyl group, benzoxazolonyl group, benzothiazolonyl group, quinazolonyl group, pyrimidyl group, quinoxalonyl group, phthalozonyl group, dioxapyrimidinyl group, pyridonyl A group, an iskylononyl group, an isoquinolinyl group, a benzisoxazolyl group, a benzisothiazolyl group, an indazolonyl group, an acridinyl group, an acridonyl group, a quinazoline dionyl group, a quinoxaline dionyl group, a benzoxanthionionyl group and a naphthalimidyl group. is there. Further, both the aromatic ring and the heterocyclic aromatic ring may have a substituent.

In the formula (1), R ₁ and R ₂ as water-insoluble substituents are, for example, linear or branched saturated or unsaturated carbon atoms having 1 to 18 carbon atoms.
Is more preferable, and an alkyl group having 1 to 12 carbon atoms is more preferable. These groups may be unsubstituted or substituted with a hydroxyl group, a halogen atom, an alkoxy group, an acyloxy group, an alkylmercapto group, an alkoxycarbonyl group or a cyano group. Examples of such a group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a secondary butyl group, a tertiary butyl group, a methylbutyl group, an n-heptyl group, an n-octyl group and a nonyl group. Group, decyl group, undecyl group, dodecyl group,
Examples thereof include stearyl group, hydroxymethyl group, trifluoromethyl group, trifluoroethyl group, cyanoethyl group, methoxycarbonylmethyl group and acetoxymethyl group. Further, R ₁ and R ₂ may be an aryl group, preferably unsubstituted or halogen atom, an alkyl group having 1 to 12 carbon atoms, or 1 to 1 carbon atom.
A compound which is a phenyl group substituted by an alkoxy group having 2 carbon atoms, an alkylmercapto group having 1 to 12 carbon atoms, a trifluoromethyl group or a nitro group, and in which R ₁ and R ₂ are hydrogen atoms is particularly preferable.

Further, a preferred compound is a compound in which A and B are the same or different and each has a group represented by the formula (2). Particularly preferred compounds are those in which in formula (3), _one of X ₁ and Y ₁ is hydrogen atom, chlorine atom, bromine atom, methyl group, cyano group, N, H-dimethylamino group, N, H. -Diethylamino group, alkoxy group having 1 to 12 carbon atoms, 1 to 12 carbon atoms
Is an alkylmercapto group or an alkoxycarbonyl group having 2 to 4 carbon atoms, and the other substituent is a hydrogen atom (1). X ₁ and Y ₁ are located at the ortho, meta or para position with respect to the dithioketopyrrolopyrrole group, and preferably located at the meta or para position.

[0018]

[Chemical 6]

The above charge generating agent forming the photoconductive layer is mixed with a binder resin to form the photoconductive layer. The mixing ratio of the binder resin is 0 to 10 parts by weight, preferably 0.1 to 1 part by weight of the binder resin to 1 part by weight of the charge generating agent.
It is desirable to use it in a ratio of parts by weight. The thickness of the charge generation layer after drying is 0.01 to 1 μm, preferably 0.1 to 0.3 μm. Further, these charge generating substances can also be used in thin film forming means such as vapor deposition and sputtering. In these methods, it is not necessary to use a binder resin and the film uniformity is excellent. For example, the above-mentioned pyrrolopyrrole-based pigments and phthalocyanine-based pigments can be exposed to a solvent atmosphere of toluene, xylene or the like after forming a film, and coating when stacking a charge transport layer without further performing such treatment. Similar changes can be made with solvents. The film thickness is 0.1 to 1 μm, preferably 0.1 to 0.5 μm.

The charge transport layer 14 "is composed of a charge transport material and a binder resin. The charge transport material is a material having a good property of transporting the charge generated by the charge generating material, and is, for example, a chemical compound described below. Oxadiazole type, oxazole type, triazole type, thiazole type, triphenylmethane type, styryl type, pyrazoline type, hydrazone type, aromatic amine type, carbazole type, which show the structure,
There are polyvinylcarbazole-based, stilbene-based, enamine-based, azine-based, amine-based, triphenylamine-based, butadiene-based, polycyclic aromatic compound-based, etc., and it is necessary to use a substance having a good hole transport property.

Preferred examples include triphenyl-based, enamine-based, hydrazone-based, butadiene-based, and stilbene-based charge transfer agents, and specifically, JP-A-62-287257.
JP-A-58-182640, JP-A-48
-43942, JP-B-34-5466, JP-A-58-198043, JP-A-57-1018.
44, JP-A-59-195660, JP-A-60-69657, JP-A-64-65555, JP-A-1-164952, and JP-A-64-57.
No. 263, Japanese Unexamined Patent Publication No. 64-68761, Japanese Unexamined Patent Publication No. 1-230055, Japanese Unexamined Patent Publication No. 1-1142654, Japanese Unexamined Patent Publication No. 1-142655, Japanese Unexamined Patent Publication No. 1-155.
The charge transport materials described in JP-A No. 358, JP-A No. 1-155357, JP-A No. 1-161245, and JP-A No. 1-142643 are mentioned. Further, in the case of transporting electrons instead of transporting holes as charges as described above, as an electron transporting substance, Japanese Patent Application No.
The electron transport material described in No. 4721 can be used.

As the binder resin, the same binder resins as those mentioned above in the charge generation layer can be used, but preferably a polycarbonate resin, a styrene resin,
It is a styrene-butadiene copolymer resin. The binder resin is 0 to 10 parts by weight with respect to 1 part by weight of the charge transport material,
It is desirable to use it in a ratio of preferably 0.1 to 1 part by weight. The thickness of the charge transport layer after drying is 1 to 50 μm, preferably 10 to 30 μm.

If necessary, a photo-sustaining conductivity imparting agent is added to the charge generation layer or the charge transport layer. The above-mentioned charge generation layer and charge transport layer have photosustainability by themselves, but this persistence-conducting agent is added for the purpose of enhancing photosustainability in the charge generation layer and charge transport layer. It is something. Examples of such a photo-sustaining conductivity imparting agent include aryl methane dyes, diazonium salts, acid anhydrides, o-benzosulfoimides, ninhydrins, cyano compounds as described in Japanese Patent Application No. 5-4721. Examples include nitro compounds, sulfonyl chlorides, diphenyl or triphenylmethanes, o-benzoylbenzoic acid, and leuco dyes. These photo-sustaining conductivity imparting agents are added in an amount of 0.001 to 1 part by weight, preferably 0.001 to 0.1 part by weight, relative to 1 part by weight of the charge generating substance.
It is added in a proportion of parts by weight. If the amount of the photo-sustaining conductivity-imparting agent added exceeds 1 part by weight, the photo-conductivity function of the photosensor is significantly deteriorated, which is not preferable.

Some of the photo-sustaining conductivity-imparting substances do not have a spectral sensitivity in the visible light region, and when optical information in the visible light region is used, in order to impart sensitivity in the visible light region. An electron accepting substance, a sensitizing dye and the like can be further added. Examples of the electron accepting substance include nitro-substituted benzene, diano-substituted benzene, halogen-substituted benzene, quinones and trinitrofluorenone. Examples of the sensitizing dye include triphenylmethane dye, pyrylium salt dye and xanthene dye. The electron accepting substance, the sensitizing dye and the like are added in a proportion of 0.001 to 1 part by weight, preferably 0.01 to 1 part by weight, relative to 1 part by weight of the charge generating substance. At the same time, when the optical information is in the infrared region, it is advisable to add a pigment such as phthalocyanine or the like, a pyrrole-based dye, a cyanine-based dye or the like in the same amount, and vice versa. in case of,
The purpose is achieved by adding the same amount of each wavelength absorbing substance.

Further, in forming the charge generating layer made of an organic compound, dichloroethane, 1,1,2-trichloroethane, chlorobenzene, tetrahydrofuran, and
Cyclohexanone, dioxane, 1,2,3-trichloropropane, ethyl cellosolve, 1,1,1-trichloroethane, dichloromethane, methyl ethyl ketone, chloroform, toluene, etc. may be used as a coating solution. The coating method may be blade coating. Method, dipping method, spinner coating method and the like.

In the sensor of the present invention, the charge injection control layer may be formed between the electrode and the charge generation layer. The charge injection control layer is provided to control the charge injection property from the electrode layer 13 to the charge generation layer 14 'in the photosensor to adjust the voltage substantially applied to the information recording medium. Such a charge injection control layer can set the sensitivity of the optical sensor in the operating voltage region of the liquid crystal, particularly when the information recording layer in the information recording medium is a polymer dispersed liquid crystal layer as described later. is necessary. That is, the difference (contrast potential) between the potential (bright potential) applied to the information recording medium in the exposed portion and the potential (dark potential) applied to the information recording medium in the unexposed portion is calculated as the operating area of the liquid crystal in the information recording medium. This is because it is necessary to take a large amount in.

Therefore, for example, the dark potential applied to the liquid crystal layer corresponding to the unexposed portion of the photosensor needs to be set to about the operation start potential of the liquid crystal. Therefore, the photosensor bulk is required to have such conductivity that a dark current of 10 ⁻⁴ to 10 ⁻⁸ A / cm ² is generated in a state where an electric field of 10 ⁵ V / cm to 10 ⁶ V / cm is applied. Is 10 ^-5 to 10 ^-6 A
The range of / cm ² is preferable. Dark current of 10 ^-8 A / cm ²
In the following optical sensors, the liquid crystal layer does not align even when exposed,
Further, in a photosensor having a dark current of 10 ⁻⁴ A / cm ² or more, a large amount of current flows simultaneously with voltage application even in an unexposed state, and even if the liquid crystal is aligned and exposed, a difference in transmittance due to exposure cannot be obtained. The charge injection control layer is appropriately provided in relation to the characteristics of such an information recording medium.

The electrode layer 13 is required to have transparency if the information recording medium described later is opaque, but if the information recording medium is transparent, it may be transparent or opaque. Materials that stably provide a surface resistivity of ⁴ Ω / cm ² , for example, metal thin film conductive films of zinc, titanium, copper, iron, tin, etc., tin oxide, indium oxide, zinc oxide, titanium oxide, tungsten oxide, vanadium oxide And the like, and organic conductive films such as a quaternary ammonium salt, which are used alone or as a composite material of two or more kinds. Of these, oxide semiconductors are preferable, and indium oxide-tin oxide composite oxide (ITO) is particularly preferable. The electrode layer 13 is formed by a method such as vapor deposition, sputtering, CVD, coating, plating, dipping, and electrolytic polymerization. The film thickness needs to be changed depending on the electrical characteristics of the material forming the electrodes and the applied voltage at the time of information recording. For example, the thickness of the ITO film is about 10 to 300 nm, and the entire surface between the information recording layer and Alternatively, it is formed according to the formation pattern of the photoconductive layer.

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

Next, the information recording system of the present invention will be described. FIG. 2 is a diagram for schematically explaining the aspect of the first information recording system by its cross section. The information recording medium 2 in which the information recording layer 11 and the electrode layer 13 ′ are sequentially laminated and the optical sensor 1 described above are shown. A spacer 19 is arranged, and a space is provided between the optical sensor and the information recording medium so as to face each other and are laminated.

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 polymer dispersed liquid crystal. The polymer-dispersed liquid crystal in the present invention has a structure in which synthetic resin particles are dispersed in the liquid crystal phase, and as the liquid crystal material, smectic liquid crystal, nematic liquid crystal, 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 a memory property that retains its orientation and permanently retains information. As the smectic liquid crystal, a liquid crystal substance exhibiting a smectic A phase such as a cyanobiphenyl type, a cyanoterphenyl type, a phenyl ester type, or a fluorine type having a long carbon chain at a terminal group of a substance exhibiting liquid crystallinity, and a ferroelectric liquid crystal Examples thereof include a liquid crystal substance exhibiting a smectic C phase, a liquid crystal substance exhibiting smectic H, G, E, F and the like.

A nematic liquid crystal may be used, and the memory property can be improved by mixing it with a smectic or cholesteric liquid crystal. For example, a Schiff base type, an azoxy type, an azo type, a benzoic acid phenyl ester type, Cyclohexyl acid phenyl ester type, biphenyl type, terphenyl type, phenyl cyclohexane type,
Known nematic liquid crystals such as phenyl pyridine type, phenyl oxazine type, polycyclic ethane type, phenyl cyclohexene type, cyclohexyl pyrimidine type, phenyl type and tolan type can be used. Also, a microcapsule obtained by mixing polyvinyl alcohol or the like with a liquid crystal material can be used. When selecting a liquid crystal material, it is preferable to use a material having a large anisotropy in the refractive index because the contrast can be obtained.

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 ester, methacrylic acid ester and the like, and in a monomer or oligomer state, for example, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, polypropylene glycol. Diacrylate, isocyanuric acid (ethylene oxide modified) triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, etc. -Based oligomer, further nonylphenol-modified acrylate, N-vinyl-2-pyrrolidone, 2-hydroxy-3-phenoxy Monofunctional monomers or oligomers such as acrylate and the like. The solvent is not particularly limited as long as it is a common solvent, for example, a hydrocarbon-based solvent represented by xylene or the like, a halogenated hydrocarbon-based solvent represented by chloroform or the like, or an alcohol derivative-based represented by methyl cellosolve or the like. Examples thereof include solvents and ether solvents such as dioxane.

Examples of the photo-curing agent for curing the UV-curable resin include 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 11 manufactured by Merck & Co., Inc.).
73), 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba-Geigy), 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one (Merck Darocur 1
116), benzyl dimethyl ketal (Irgacure 651 manufactured by Ciba-Geigy), 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropanone-1 (Ciba-Geigy Irgacure 907),
A mixture of 2,4-diethylthioxanthone (Kayacure DETX manufactured by Nippon Kayaku Co., Ltd.) and ethyl p-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), isopropylthioxanthone (KuntaCure ITX manufactured by Ward Brekinsop), and Examples thereof include a mixture with ethyl p-dimethylaminobenzoate, but liquid 2-hydroxy-2-methyl-1-phenylpropan-1-one is compatible with a liquid crystal material, a polymer-forming monomer or an oligomer. Is particularly preferable in terms of.

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.
It is preferable to use it in an amount of 80% by weight, and if it is less than 10% by weight, the light transmittance is low even if the liquid crystal phase is oriented by information recording, and if it exceeds 90% by weight, a phenomenon such as liquid crystal seepage occurs. Occurs, and image unevenness occurs, which is not preferable. A large amount of liquid crystal is present in the information recording phase to improve the contrast ratio and reduce the operating voltage.

The information recording layer is formed by coating the electrode layer with a mixed solution prepared by dissolving or dispersing a resin-forming material, liquid crystal, and a photo-curing agent in a solvent, such as a blade coater, roll coater, or spin coater. Apply by the method,
It is formed by curing the resin forming material with light or heat. If necessary, a leveling agent may be added to improve the coating suitability of the solution and improve the surface property.

In forming the information recording layer, the mixed solution is heated to a temperature at which the mixed liquid of the resin-forming material and the liquid crystal maintains an isotropic phase so that the liquid crystal and the ultraviolet-curable resin-forming material are completely compatible with each other. Therefore, it is possible to obtain an information recording layer in which a resin phase and a liquid crystal phase are uniformly dispersed. If the liquid crystal is UV-cured at a temperature below the isotropic phase, there arises a problem that the phase separation between the liquid crystal and the UV-curable resin material becomes large. That is, the liquid crystal domain grows too much, the skin layer is not completely formed on the surface of the information recording layer, the phenomenon of liquid crystal bleeding occurs, and the ultraviolet curable resin becomes matte, making it difficult to accurately capture information. However, it is not preferable, and the ultraviolet curable resin may not be able to hold the liquid crystal, and may not even form the information recording layer. On the other hand,
When heating the solvent to evaporate the solvent to maintain the isotropic phase, the wettability with respect to the electrode layer is reduced,
There is a problem that a uniform information recording layer cannot be obtained.

A fluorine-based surfactant may be added to the information recording layer for the purpose of maintaining the wettability with respect to the electrode layer and forming a film on the surface of the resin. Examples of such a fluorine-based surfactant include Fluorard FC-430 and Fluorard FC, manufactured by Sumitomo 3M Limited.
-431, N- (n-propyl) -N- (β-acryloxyethyl) -perfluorooctylsulfonic acid amide (EF-125M manufactured by Mitsubishi Materials Corporation), N- (n
-Propyl) -N- (β-methacryloxyethyl) -perfluorooctylsulfonic acid amide (EF-135M manufactured by Mitsubishi Materials Corporation), perfluorooctanesulfonic acid (EF-101 manufactured by Mitsubishi Materials Corporation), per Fluorocaprylic acid (MF-2 manufactured by Mitsubishi Materials Corporation)
01), N- (n-propyl) -N-perfluorooctane sulfonic acid amide ethanol (EF-121 manufactured by Mitsubishi Materials Corp.), EF-102, EF-103, and EF manufactured by Mitsubishi Materials Corp. -104, same E
F-105, EF-112, EF-121, EF
-122A, EF-122B, EF-122C, EF-122A3, EF-123A, EF-123
B, the same EF-132, the same EF-301, the same EF-30
3, the same EF-305, the same EF-306A, the same EF-50
1, the same EF-700, the same EF-201, the same EF-20
4, the same EF-351, the same EF-352, the same EF-80
1, the same EF-802, the same EF-125DS, the same EF-1
200, EF-L102, EF-L155, EF
-L174, EF-L215 and the like. Also,
3- (2-perfluorohexyl) ethoxy-1,2-
Dihydroxypropane (MF-made by Mitsubishi Materials Corporation)
100), N-n-propyl-N-2,3-dihydroxypropyl perfluorooctyl sulfonamide (MF-110 manufactured by Mitsubishi Materials Corporation), 3- (2-perfluorohexyl) ethoxy-1,2-epoxy. Propane (MF-120 manufactured by Mitsubishi Materials Corporation), Nn-propyl-N-2,3-epoxypropyl perfluorooctylsulfonamide (MF- manufactured by Mitsubishi Materials Corporation)
130), perfluorohexylethylene (MF-140 manufactured by Mitsubishi Materials Corporation), N- (3-trimethoxysilyl) propyl) perfluoroheptylcarboxylic acid amide (MF-150 manufactured by Mitsubishi Materials Corporation), N-
(3-trimethoxysilyl) propyl) perfluoroheptylsulfonamide (MF-manufactured by Mitsubishi Materials Corp.)
160) and the like. The fluorine-based surfactant is added in a proportion of 0.1 to 20% by weight based on the total amount of the liquid crystal and the resin forming material.

Further, the solid content concentration in the coating solution in forming the information recording layer is preferably 10 to 60% by weight, and at the time of curing, the curing conditions such as the kind and concentration of the resin, the coating layer temperature, and the ultraviolet irradiation conditions are appropriately selected. By setting
It is possible to favorably form a skin layer consisting only of a resin layer having no liquid crystal phase as the outer skin layer, which can increase the proportion of liquid crystal used in the information recording layer,
Further, it is possible to prevent the liquid crystal from seeping out. The UV-curable resin has been described above as the resin material, but other solvent-soluble thermosetting resins having compatibility with the same solvent as the liquid crystal material, such as acrylic resin, methacrylic resin, polyester resin, polystyrene resin, Also, a copolymer mainly composed of these, an epoxy resin, a silicone resin or the like may be used. Since the film thickness of the information recording layer affects the resolution, the film thickness after drying may be 0.1 μm to 10 μm, preferably 3 μm to 8 μm, and the operating voltage should be lowered while maintaining high resolution. You can If the film thickness is too thin, the contrast of the information recording portion will be low, and if it is too thick, the operating voltage will be high, which is not preferable.

When the information recording layer itself has a supporting property and the support is omitted, a skin layer is formed on the surface of the information recording layer. Even if laminated by a method or the like, cracking does not occur and the conductivity is not lowered. In this case, it is advisable to form the information recording medium by peeling off the temporary support after providing the electrode layer on the information recording layer provided on the temporary support.

The electrode layer 13 'in the information recording medium is provided on the substrate 15 by using the same material as that of the electrode layer 13 in the above-described photosensor and the same laminating method. As shown in FIG. 2, this information recording medium is arranged so as to face the above-mentioned optical sensor via a spacer 19, and both electrode layers 13 and 1 are provided.
3'is connected via a voltage source V to form a first information recording system. Electrode layers 13, 13 'in this system
It suffices that either one or both of them be transparent.

As the spacer, a resin film of polyester such as polyethylene terephthalate, polyimide, polyethylene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyamide, polypropylene, cellulose acetate, ethyl cellulose, polycarbonate, polystyrene, polytetrafluoroethylene, etc. It may be formed by using, or may be formed by applying and drying each of the above resin solutions. Also aluminum,
It may be formed by vapor deposition of a metal material such as selenium, tellurium, gold or platinum, or an inorganic or organic compound. The film thickness of the spacer is the gap distance between the optical sensor and the information recording medium,
Since it affects the voltage distribution applied to the information recording layer,
At least 100 μm or less is preferable, and 3 is preferable.
It is good to set it to 30-30 micrometers.

Next, the second information recording system will be described. FIG. 3 is a sectional view showing a second information recording system of the present invention, in which 20 is a dielectric layer,
The same reference numerals as those in FIG. 2 indicate the same contents. In the second information recording system, the optical sensor and the information recording medium in the first information recording system are arranged so as to face each other with the dielectric layer 20 in between, and are directly laminated. The second information recording system 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 It is possible to prevent image unevenness due to liquid crystal elution in the information recording layer, or elution of the photoconductive material by the solvent for forming the information recording layer, and it is possible to integrate the optical sensor and the information recording medium. It is what

When forming the dielectric layer 20, it is necessary that the dielectric layer 20 is not soluble in both the photoconductive layer forming material and the information recording layer forming material, and it is also necessary that it is not conductive. Is. In the case of having conductivity, the space charge is diffused and the resolution is deteriorated, so that the insulating property is required. Further, the dielectric layer lowers the distribution voltage applied to the liquid crystal layer or deteriorates the resolution. Therefore, it is preferable that the film thickness is thin, and it is preferable that the film thickness be 2 μm or less. In addition to the generation of image noise due to various interactions, there is a problem of penetration due to defects such as pinholes in the multilayer coating. 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.
The following film thickness is preferable, and 0.1 to 3 μm is preferable. Further, in consideration of the voltage distribution applied to each layer, it is preferable to use a material having a high dielectric constant as well as a thin film.

As a material for forming the dielectric layer, inorganic materials such as SiO ₂ , TiO ₂ , CeO ₂ , Al ₂ O ₃ , GeO ₂ , Si ₃ N ₄ and AlN are used.
, TiN, etc., and may be formed by stacking by a vapor deposition method, a sputtering method, a chemical vapor deposition (CVD) method, or the like. Also,
Water-soluble resin having low compatibility with organic solvents, for example, polyvinyl alcohol, water-based polyurethane, using an aqueous solution such as water glass, spin coating method, blade coating method,
You may laminate | stack by a roll coat method etc. Further, a coatable fluororesin may be used, and in this case, it may be dissolved in a fluorine-based solvent and coated by a spin coating method, or laminated by a blade coating method, a roll coating method or the like. The applicable fluororesin is, for example, JP-A-1-1.
Fluorine resins disclosed in Japanese Patent No. 31215 and the like, and organic materials such as polyparaxylylene film-formed in a vacuum system can be preferably used.

The outline of the information recording system according to the present invention has been described above. Now, the amplifying action of the photocurrent in the photosensor will be described. As an optical sensor for measurement, an ITO electrode layer is provided on a transparent glass substrate, and a photoconductive layer is laminated on the electrode layer. In the optical sensor, 0.16 cm ² is formed on the photoconductive layer. It is formed by stacking gold electrode layers having a thickness of 10 nm and a surface resistance of 1 kΩ / □. Then, a constant DC voltage is applied between both electrodes, and 0.5 seconds after the start of voltage application, light is irradiated from the substrate side for 0.033 seconds, and the behavior of the current value in the photosensor during the measurement time is measured by light irradiation. Measure from the start (t = 0). It should be noted that the irradiation light is selected by irradiating green light with a xenon lamp (L2274 manufactured by Hamamatsu Photonics Co., Ltd.) as a light source using a green filter (manufactured by Nippon Vacuum Optical Co., Ltd.).
Irradiation light intensity is measured with an illuminometer (manufactured by Minolta Co., Ltd.) to obtain 20 lux. FIG. 4 shows the filter characteristics.

When irradiated with light at this light intensity, the transparent substrate, I
Considering the light transmittance of the TO 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 photocurrent of 1.35 × 10 ⁻⁶ A / cm ² is generated per unit area.

Here, the ratio of the photo-induced current actually generated by the photosensor to the theoretical photocurrent when measured by the above measurement system (the photo-induced current value actually generated by the photosensor / theoretical The photocurrent value) is defined as the quantum efficiency of the photosensor. In addition, the photo-induced current is a value obtained by subtracting the dark current value from the current value of the light irradiation part, and a current that exceeds the dark current due to light irradiation flows during voltage irradiation or during light irradiation with a voltage applied. Yes, it is different from so-called photocurrent. The photocurrent amplification action in the photosensor of the present invention is defined as such behavior of photoinduced current.

An optical sensor having a photocurrent amplifying action and an optical sensor having no photocurrent amplifying action (hereinafter referred to as a comparative sensor) according to the present invention will be described using the measurement results of the above measurement system. First, the measurement results of the comparative sensor are shown in FIG. In FIG. 5, line (m) is a reference line indicating the above theoretical value (1.35 × 10 ⁻⁶ A / cm ² ), and light irradiation is performed for 0.033 seconds, and voltage application is continued after light irradiation. Indicates. Line (n) is a measured line of a photosensor that does not have a photocurrent amplification effect, and it is found that the photocurrent does not increase even during light irradiation and takes a constant value. The constant value is also a theoretical value (1.35 × 10 ^−6). A / cm ² ) is not exceeded. The quantum efficiency of this comparative sensor is constant at approximately 0.4. The change in quantum efficiency during light irradiation is shown in FIG. On the other hand, in the optical sensor of the present invention, as shown in FIG. 7, the photocurrent increases during light irradiation, and as is clear from FIG. 8 showing the relationship with the quantum efficiency, as shown in FIG. Efficiency exceeds 1,
It can be seen that the quantum efficiency continues to increase thereafter.

Further, in the comparison sensor, the photocurrent becomes zero at the same time when the light irradiation is completed, so that the current does not flow even if the voltage is continuously applied after the light irradiation. On the other hand, in the photosensor of the present invention, the photoinduced current continues to flow by continuing the voltage application even after the end of the light irradiation, and the photoinduced current can be subsequently taken out.

FIG. 9 shows the change over time of the integrated value (charge amount) of the current amount of the comparative sensor (theoretical value). In the figure,
The time change of the integrated value of the current amount per unit area in the theoretical optical sensor with the quantum efficiency of 1 is shown by the (O) line, and the time change of the integrated value of the current amount per unit area in the comparative sensor is shown by the (P) line. Show. The integrated value Q of the current in FIG. 9 is Q = ∫ (I _PHOTO −I _dark ) dt (C). From the figure, the comparison sensor shows that after the light irradiation, I
_{Since PHOTO-} I _dark is zero, no increase in the integrated value is seen. Further, FIG. 10 similarly shows the time change of the integrated value of the current per unit area in the optical sensor of the present invention.
Similarly, the time change of the integrated value of the current per unit area in the theoretical photosensor with quantum efficiency of 1 is indicated by the (O) line, and the time change of the integrated value of the current in the photosensor of the present invention is indicated by the (P) line. Indicate. As shown in the figure, it can be seen that the optical sensor of the present invention continues to increase even after the end of light irradiation, so that a large effect can be obtained as compared with the comparative sensor.

Next, the information recording method in the first and second information recording systems of the present invention will be described. Figure 11
FIG. 6 is a diagram for explaining an information recording method in the first information recording system of the present invention. The same applies to the second information recording system. In the figure, 11 is an information recording layer, 13
Is an electrode layer of an optical sensor, 13 'is an electrode layer of an information recording medium, 14 is a photoconductive layer, 21 is a light source, 22 is a shutter having a driving mechanism, 23 is a pulse generator (power source), and 24 is a dark box. When information light is incident from the light source 21 while applying a voltage by the pulse generator 23 between the electrode layers 13 and 13 ', photocarriers generated in the photoconductive layer 14 at the portion where the light is incident are formed by both electrodes. Is moved to the interface on the information recording layer 11 side by the generated electric field,
The voltage is redistributed, the liquid crystal phase in the information recording layer 11 is aligned, and recording is performed according to the pattern of the information light. Further, since the operating voltage and range vary depending on the liquid crystal, when setting the applied voltage and the applied voltage time, the voltage distribution in the information recording medium is appropriately set, and the voltage distribution applied to the information recording layer is set to the operating voltage of the liquid crystal. It is recommended to set it in the area.

The information recording method of the present invention is capable of planar analog recording and can obtain recording at the liquid crystal level.
High-resolution recording is performed, and the exposure pattern is retained as a visible image due to the orientation of the liquid crystal phase.

As a form of the information recording system, 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 instead of a photographic film used in a normal camera, which is used as a recording member, and an optical shutter can also be used.
An electric shutter can also be used. Also,
R, R
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,
Color images can also be taken by recording each image of B and forming one frame.

The laser recording method is as follows.
Argon laser (514.488n)
m), a helium-neon laser (633 nm), a semiconductor laser (780 nm, 810 nm, etc.) can be used,
Laser exposure corresponding to an image signal, a character signal, a code signal, and a line drawing signal is performed by scanning. An analog recording such as an image is performed by modulating the light intensity of the laser, and a digital recording such as a character, a code or a line drawing is performed by ON / OFF control of the laser light. In the case of halftone dot formation in an image, laser light is subjected to dot generator ON-OFF control. The spectral characteristic of the photoconductive layer in the optical sensor does not need to be panchromatic, and may be sensitive 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 system as shown in FIG. 12, and is kept as it is in the case of the second information recording system. When the information is reproduced by the transmitted light, the light A is transmitted because the liquid crystal is oriented in the direction of the electric field in the information recording portion, while the light B is scattered in the portion where the information is not recorded and the information recording portion The contrast can be taken.
Further, it may be read by reflected light through the light reflecting layer. Specifically, in the case of the first information recording system, the electrode of the information recording medium may be of a light reflecting type such as aluminum, or the dielectric mirror layer may be provided between the electrode and the liquid crystal layer,
In the case of the second information recording medium, by using a dielectric mirror layer as the dielectric layer, reflection reading becomes possible. The information recorded by the orientation of the liquid crystal is visible information that can be visually read, but it can also be read by enlarging it with a projector, and can read the information with high accuracy using laser scanning or a CCD. . If necessary, scattered light can be prevented by using a Schlieren optical system. As described above, as the information recording medium, the recording by the information exposure is visualized by the orientation of the liquid crystal. By selecting the combination of the liquid crystal and the resin,
It is possible to impart memory property without erasing the information that is once oriented and visualized. Further, by heating to a high temperature near the isotropic phase transition, the memory 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, an electrostatic information recording medium having a charge holding layer as an information recording layer described in JP-A-3-7942 may be used. Since information is stored in the information recording medium in the form of electrostatic charges, the electrostatic charges are developed by toner, or the electrostatic charges are stored in, for example, JP-A 1-2.
It can be reproduced by potential reading as described in Japanese Patent No. 90366. In addition, JP-A-4-4634
An information recording medium having a thermoplastic resin layer as an information recording layer may be used, which is described in Japanese Patent No. 7 or the like, and in this case,
After the information is accumulated on the surface in the form of electrostatic charge in the same manner as described above, the thermoplastic resin layer is heated, whereby the information is accumulated as a frosted image and can be reproduced as visible information.

[0058]

According to the present invention, an optical sensor in which an electrode layer is provided on a substrate and a photoconductive layer is laminated on the electrode layer, and an information recording layer capable of recording information by an electric field or electric charge is laminated on the electrode layer A photoconductive layer containing a compound having a specific chemical structure in an optical sensor in an information recording system for recording information on a recording medium by recording information in a state where a voltage is applied between both electrodes and a recording medium facing each other. I used
The amplification factor of the optical sensor increases, enabling highly sensitive information recording, and even after the light irradiation ends, if the voltage is continuously applied, its conductivity is maintained, and the electric field or the charge amount corresponding to the light irradiation amount. Since it has a function of imparting the above electric field or charge amount to the information recording medium, it is possible to record information with higher sensitivity.

[0059]

EXAMPLES Examples of the present invention will be described below. Example 1 A film having a thickness of 1 was formed on a 1.1 mm-thick glass substrate that had been thoroughly washed.
An ITO film of 00 nm was formed by sputtering to obtain an electrode layer. On the electrode, the following structure as a charge generating agent

[0060]

[Chemical 7]

4 parts by weight of a pyrrolopyrrole pigment having 1 part by weight of polyvinyl butyral resin (BMS: Sekisui Chemical Co., Ltd.) and 120 parts by weight of 1,2-dichloroethane are mixed and dispersed for 3 hours with a paint shaker. To obtain a coating solution, which is applied with a spinner at 3000 rpm for 0.4 seconds and then dried at 100 ° C. for 1 hour to give a film thickness of 300 nm.
Of the charge generation layer. On this charge generation layer, the following structure is used as a charge transfer agent.

[0062]

[Chemical 8]

3 parts by weight of the enamine derivative of, polystyrene resin (HRM-3 manufactured by Denki Kagaku Kogyo KK), 2 parts by weight,
Using a spinner, apply a coating solution prepared by mixing 22 parts by weight of 1,1,2-trichloroethane and 14 parts by weight of dichloromethane with a spinner.
The photosensor in the present invention having a photoconductive layer having a film thickness of 20 μm, which is composed of a charge generation layer and a charge transport layer, after being coated at 00 rpm for 0.4 seconds and dried at 80 ° C. for 2 hours. Got

(Electrical Characteristics of Optical Sensor) In order to measure the electrical characteristics of the optical sensor obtained above, a thickness of 300 nm and an area of 0.16 cm were formed on the charge transport layer of the optical sensor.
^{A second} gold layer was vapor-deposited to form a counter electrode and a measurement medium, and a current measurement system as shown in FIG. 13 was constructed. In the figure, 15 is a substrate of an optical sensor, 13 is an electrode layer of the optical sensor, 14 is a photoconductive layer including a charge generation layer and a charge transport layer, 30 is a gold electrode, 31 is a light source, 32 is a shutter (No. ．
0 electromagnetic shutter), 33 is a shutter drive mechanism, 3
4 is a pulse generator (made by Yokogawa Hewlett Packard), 35 is an oscilloscope (VC-6 made by Yokogawa Hewlett Packard).

In this current measuring system, the electrode layer 13 in the photosensor is positive, the gold electrode is negative, and the distance between the electrodes is 3
At the same time as applying a DC voltage of 00V, 1/30 from the glass substrate side through R, G, and B filters, respectively.
Exposed for 2 seconds. The exposure illuminance was such that R, G, and B were 1.1 lux, 20 lux, and 1.3 lux, respectively. The voltage application was continued for 0.15 seconds, and the time change of the current during that time was measured by an oscilloscope. In addition, current was measured in the same manner by applying voltage only without exposure. The obtained results are shown in FIG. The horizontal axis represents voltage application time (seconds), and the vertical axis represents current density (μA / cm ² ). With the optical sensor of the present invention, the amount of current is two inflection points (a).
(B) is observed. The amount of current below the inflection point (a) is
From the comparison with the optical sensor described in Comparative Example 1 described later,
It is considered to be the amount of current (hereinafter referred to as photocurrent) according to the exposure amount, and the current above the inflection point (a) is considered to be the amount of current due to amplification by the optical sensor. Further, the inflection point (b) is a change point of the current amount with the end of the exposure, and the current (hereinafter,
It can be seen that the photo-induced current) continuously flows and is gradually attenuated. That is, from this figure, in the photosensor of the present invention, the photocurrent continues to increase during exposure, and
It can be seen that the effective current continues after the exposure, and decays after a sufficient time.

(Information Recording Performance of Optical Sensor) As shown in FIG. 14, the above-mentioned measuring optical sensor and the condenser C ₁
(160 pF), resistance R ₁ (1000 MΩ), power supply (E), and voltmeter (V) were used to prepare a voltage measurement circuit. The capacitor and the resistor correspond to the information recording medium. At the same time when an external voltage is applied to this measurement circuit, 20 lux of light (wavelength 550 nm) is emitted from the optical sensor side for 1/30
Exposed for 2 seconds. The voltage application continued for 0.15 seconds. The applied voltage was set so that the potential of the unexposed portion was 200 V when the potential difference (ΔV) between the exposed portion and the unexposed portion was maximum. The results are shown in Fig. 16. The maximum potential differences were 105V, 123V, and 100V for R, G, and B, respectively. The applied voltage was 550 V and 80 msec in all cases.

Example 2 A charge transport agent having the following chemical structure

[0068]

[Chemical 9]

An optical sensor was manufactured in the same manner as in Example 1 except that a compound was used, and the green light of R, G, B was used in the same manner as in Example 1 to obtain the electrical characteristics of the optical sensor. Was measured, and the results are shown in FIG. 17 and the information recording characteristics are shown in FIG. The maximum potential difference was 104 V, the applied voltage was 610 V, and 140 msec. Example 3 A charge transport agent having the following chemical structure

[0070]

[Chemical 10]

An optical sensor was manufactured in the same manner as in Example 1 except that a compound was used, and the green light of R, G, B was used in the same manner as in Example 1 to obtain the electrical characteristics of the optical sensor. Was measured, and the results are shown in FIG. 17 and the information recording characteristics are shown in FIG. The maximum potential difference was 84.9 V, the applied voltage was 630 V, and 100 msec.

Example 4 A charge transport agent having the following chemical structure

[0073]

[Chemical 11]

An optical sensor was manufactured in the same manner as in Example 1 except that a compound was used, and the green light of R, G, B was used in the same manner as in Example 1 to obtain the electrical characteristics of the optical sensor. Was measured, and the results are shown in FIG. 20 and the information recording characteristics are shown in FIG. The maximum potential difference was 112 V, the applied voltage was 450 V, and 65 msec. Example 5 A charge transport agent having the following chemical structure

[0075]

[Chemical 12]

An optical sensor was manufactured in the same manner as in Example 1 except that a compound was used, and the green light of R, G, B was used in the same manner as in Example 1 to obtain the electrical characteristics of the optical sensor. Was measured, and the results are shown in FIG. 20 and the information recording characteristics are shown in FIG. The maximum potential difference was 101 V, the applied voltage was 450 V, and 65 msec.

Example 6 A charge transport agent having the following chemical structure

[0078]

[Chemical 13]

An optical sensor was manufactured in the same manner as in Example 1 except that the compound was used, and the electrical characteristics of the optical sensor were measured in the same manner as in Example 1 using green light.
The results are shown in FIG. 20, and the information recording characteristics are shown in FIG.
3 shows. Maximum potential difference is 95V, applied voltage is 44
It was 0 V and 70 msec.

Example 7 A film having a thickness of 10 was formed on a thoroughly washed glass substrate having a thickness of 1.1 mm.
An ITO film of 0 nm was formed by sputtering to obtain an electrode. A pyrrolopyrrole pigment having the same structure as in Example 1 was vapor-deposited on the electrode at a rate of 3 nm / sec under a vacuum of 10 ⁻⁶ torr to form a 200 nm charge generation layer. After leaving this in acetone vapor for 1 hour, a charge transport layer was laminated in the same manner as in Example 1. The electrical characteristics were measured in the same manner as in Example 1, and the results are shown in FIG.
In addition, in the imaging evaluation, good printed matter was obtained.

Comparative Example 1 Polyvinylcarbazole having the following structure and the following chemical structure

[0082]

[Chemical 14]

2,4,7-trinitrofluorenone (T
NF) was adjusted to 1: 1 (molar ratio) in tetrahydrofuran to prepare a solution having a solid content of 19% by weight, and this solution was applied onto a transparent electrode made of ITO having a thickness of 50 nm and a surface resistance of 80 Ω / □. It was applied with a blade coater at intervals of 50 μm and dried at 80 ° C. for 2 hours to obtain an optical sensor having a film thickness of 5 μm. The electrical characteristics of the photosensor were measured in the same manner as in Example 1 using 100 lux of green light. The results are shown in FIG. 25, but the sensitivity was extremely low.

Comparative Example 2 A film having a thickness of 1 was formed on a 1.1 mm-thick glass substrate that had been thoroughly washed.
An ITO film of 00 nm was formed by sputtering to obtain an electrode layer. On the electrode, the following structure as a charge generating agent

[0085]

[Chemical 15]

Bisazo pigment having 3 parts by weight, polyvinyl butyral 1 part by weight, 1,4-dioxane 98 parts by weight, and cyclohexanone 98 parts by weight are mixed and dispersed with a paint shaker for 6 hours to prepare a coating solution, which is spun at 1400 rpm. , After applying for 0.4 seconds, 100 ℃, 1
After drying for an hour, a charge generation layer having a film thickness of 300 nm was laminated. On this charge generation layer, the following structure is used as a charge transfer agent.

[0087]

[Chemical 16]

A coating liquid prepared by mixing 3 parts by weight of the compound of 2 parts by weight, 2 parts by weight of a polycarbonate resin, 22 parts by weight of 1,1,2-trichloroethane and 14 parts by weight of dichloromethane was applied by a spinner at 400 rpm for 0.4 seconds. After 8
A charge transport layer was laminated by drying at 0 ° C. for 2 hours to obtain a photosensor according to the present invention having a photoconductive layer having a film thickness of 20 μm and comprising a charge generation layer and a charge transport layer. The electrical characteristics of the obtained optical sensor were measured in the same manner as in Example 1, and the results are shown in FIG. Although it can be seen that the light of each color of R, G, and B was amplified, the contrast current was smaller than that of the example, and the currents of R, G, and B were also different from each other. Also, regarding information recording characteristics,
Each of the R, G, and B lights was measured in the same manner as in Example 1, and the results are shown in FIG. Voltage application is 570
V, 60 msec. The potential difference (ΔV) is R: 13.6
It was V, G: 33.1V, B: 22.6V.

[0089]

INDUSTRIAL APPLICABILITY The present invention provides an optical sensor in which an electrode layer is provided on a base material and a photoconductive layer is laminated on the electrode layer, and an information recording layer capable of recording information by an electric field or electric charge is laminated on the electrode layer. A photoconductive layer containing a pyrrolopyrrole compound is used in an optical sensor in an information recording system for recording information on an information recording medium by recording information in a state where a voltage is applied between both electrodes. As a result, the amplification factor of the optical sensor increases, enabling highly sensitive information recording, and even when the light irradiation is terminated, the conductivity is maintained if voltage is continuously applied, and the electric field equivalent to the light irradiation amount is maintained. Alternatively, it is possible to record information with high sensitivity by using an optical sensor having a function of giving an electric field or an electric charge larger than the electric charge to the information recording medium.

[Brief description of drawings]

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

FIG. 2 is a sectional view for explaining the first information recording system of the present invention.

FIG. 3 is a sectional view illustrating a second information recording system of the present invention.

FIG. 4 is a diagram showing a spectral characteristic of a green filter used in a measurement system used for explaining a photocurrent amplification effect of the photosensor of the present invention.

FIG. 5 is a diagram illustrating a measurement result of a photocurrent amplification effect of a comparative sensor.

FIG. 6 is a diagram showing a change in quantum efficiency of a comparative sensor during light irradiation.

FIG. 7 is a diagram illustrating a photocurrent amplification action in the photosensor of the present invention.

FIG. 8 is a diagram showing changes in quantum efficiency of the photosensor of the present invention during light irradiation.

FIG. 9 is a diagram illustrating a change over time of an integrated value (charge amount) of a current amount in a comparative sensor.

FIG. 10 is a diagram illustrating a change with time of an integrated value (charge amount) of a current amount in the photosensor of the present invention.

FIG. 11 is a diagram illustrating an information recording method of the present invention.

FIG. 12 is a diagram for explaining a method of reproducing recorded information in the information recording system of the present invention.

FIG. 13 is a diagram illustrating a measurement circuit used to evaluate the electrical characteristics of the photosensor according to the present invention.

FIG. 14 is a diagram showing electrical characteristics of an example of the optical sensor of the present invention.

FIG. 15 is a diagram for explaining a measurement circuit used to evaluate the electrical characteristics of the optical sensor of the present invention.

FIG. 16 is a diagram showing information recording characteristics of an example of the optical sensor of the present invention.

FIG. 17 is a diagram showing electrical characteristics of another embodiment of the optical sensor of the present invention.

FIG. 18 is a diagram showing information recording characteristics of another embodiment of the optical sensor of the present invention.

FIG. 19 is a diagram showing information recording characteristics of another embodiment of the optical sensor of the present invention.

FIG. 20 is a diagram showing electrical characteristics of another optical sensor according to the present invention.

FIG. 21 is a diagram showing information recording characteristics of another embodiment of the optical sensor of the invention.

FIG. 22 is a diagram showing information recording characteristics of another embodiment of the optical sensor of the present invention.

FIG. 23 is a diagram showing the information recording characteristics of another embodiment of the optical sensor of the present invention.

FIG. 24 is a diagram showing electrical characteristics of another embodiment of the optical sensor of the invention.

FIG. 25 is a diagram showing electrical characteristics of a photosensor of a comparative example.

FIG. 26 is a diagram showing electrical characteristics of a photosensor of a comparative example.

FIG. 27 is a diagram showing an information recording characteristic of an optical sensor of a comparative example.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Optical sensor, 2 ... Information recording medium, 11 ... Information recording layer, 13, 13 '... Electrode layer, 14' ... Charge generation layer, 1
4 ″ ... charge transport layer, 15 ... substrate, 19 ... spacer, 2
0 ... Dielectric layer, 21 ... Light source, 22 ... Shutter having drive mechanism, 23 ... Pulse generator (power supply), 24
... dark box, 30 ... gold electrode, 31 ... light source, 32 ... shutter, 33 ... shutter drive mechanism, 34 ... pulse generator (power supply), 35 ... oscilloscope

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Minoru Utsumi 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Dai Nippon Printing Co., Ltd.

Claims (3)

[Claims] 1. An optical sensor comprising an electrode layer provided on a base material and a photoconductive layer laminated on the electrode layer, and an information recording layer capable of recording information by an electric field or electric charge on the electrode layer. A photoconductive layer of an optical sensor used in an information recording system which is arranged so as to face the information recording medium and is capable of recording information on the information recording medium by exposing the information in a state where a voltage is applied between both electrode layers. Which contains a pyrrolopyrrole compound represented by the following chemical structural formula. [Chemical 1] In the above chemical structural formulas, A and B represent the same or different alkyl groups, aralkyl groups, cycloalkyl groups, carbocyclic or heterocyclic aromatic groups, and R ₁ ,
R ₂ represents a hydrogen atom or a substituent that does not impart water solubility. 2. An optical sensor in which an electrode layer and a photoconductive layer are laminated on a base material, and the electric field strength or the amount of electric charge applied to the information recording medium is amplified with the irradiation of light, and even after the irradiation of light is completed. 2. The photosensor according to claim 1, wherein the photosensor has a function of continuing its conductivity when a voltage is continuously applied and continuously applying an electric field strength or a charge amount to the information recording medium. 3. An optical sensor having a photoconductive layer containing a pyrrolopyrrole compound represented by the following chemical structural formula on an electrode layer formed on a base material, and information can be recorded by an electric field or electric charge on the electrode layer. And an information recording medium formed by stacking various information recording layers are arranged to face each other, and information recording can be performed on the information recording medium by information exposure in a state where a voltage is applied between both electrode layers. Information recording system. [Chemical 2] In the above chemical structural formulas, A and B represent the same or different alkyl groups, aralkyl groups, cycloalkyl groups, carbocyclic or heterocyclic aromatic groups, and R ₁ ,
R ₂ represents a hydrogen atom or a substituent that does not impart water solubility.