JP3344765B2 - Optical sensor and information recording system - Google Patents

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 on an information recording medium in the form of visible information or electrostatic information and an information recording medium, and further to an information recording method. More particularly, the present invention relates to an optical sensor and an information recording system in which information recording performance on an information recording medium is significantly amplified.

[0002]

2. Description of the Related Art An optical sensor comprising a photoconductive layer provided with an electrode layer on the front surface and an information recording medium comprising a charge holding layer provided on the rear surface with an electrode layer facing the optical sensor are arranged on an optical axis. To expose while applying a voltage between both conductive layers,
A method of recording an electrostatic charge on a charge holding layer according to an incident optical image and developing the electrostatic charge by toner development or potential reading is disclosed in, for example, JP-A-1-29036.
No. 6, JP-A-1-289975. Further, the charge retention 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. Is visualized in, for example, JP-A-3-192288.

Further, the present applicants have made the information recording layer of the above information recording medium a polymer dispersed liquid crystal layer, exposed in the same manner as described above when applying a voltage, and oriented the liquid crystal layer by an electric field formed by an optical sensor. An information recording / reproducing method for reproducing information as visible information by using transmitted light or reflected light when reproducing the information recording is firstly filed (Japanese Patent Application Nos. 2-186023 and 3-10847). did. This information recording / reproducing method can visualize recorded information without using a deflection plate.

[0004]

SUMMARY OF THE INVENTION The present invention relates to 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 task is to provide a system.

[0005]

An optical sensor according to 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 charge is laminated on the electrode layer The photoconductive layer of an optical sensor used in an information recording system that enables information recording on an information recording medium by exposing information in a state where a voltage is applied between both electrode layers has the following formula ( An optical sensor containing the pyrrolopyrrole compound represented by 1) and an enamine derivative as a charge transport substance.

[0006]

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In the above chemical structural formula, A and B
Represents the same or different alkyl group, aralkyl group, cycloalkyl group, carbocyclic or heterocyclic aromatic group, and R ₁ and R ₂ represent a hydrogen atom or a substituent that does 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 intensity or the amount of charge applied to the information recording medium is amplified with light irradiation, and a voltage is applied even after the light irradiation is completed. An optical sensor having the function of maintaining its conductivity as it continues to operate and of continuously applying an electric field intensity or a charge amount to an information recording medium. Also,
A photosensor having a photoconductive layer containing a pyrropyrrole compound represented by the above chemical structural formula on an electrode layer formed on a base material and containing an enamine derivative as a charge transporting substance, and an electric field or An information recording medium formed by laminating information recording layers capable of recording information with electric charges is arranged to face each other, and information can be recorded on the information recording medium by exposing information with a voltage applied between both electrodes. Information recording system.

Hereinafter, the present invention will be described in detail. First, in the optical sensor 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) at an irradiated portion when irradiated with light, and the carriers can move the layer width. Although the effect is remarkable when it is present, the optical sensor of the present invention can be applied to an information recording medium when irradiating light to the optical sensor by appropriately combining a photoconductive layer and an electrode layer described below. The applied electric field or electric charge is amplified as the light is irradiated, and the conductivity is maintained when the voltage is continuously applied even after the light irradiation is completed,
This has the function of continuing to apply the electric field strength or the charge amount to the information recording medium.

FIG. 1 is a cross-sectional view illustrating an optical sensor according to the present invention, and shows 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 transporting layer 14 ". A photogenerating layer 14' forming the photoconductive layer of the photosensor of the present invention is a pyrrolopyrrole compound represented by the following chemical structural formula. It contains.

[0010]

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In the above chemical structural formula, A and B
Represents the same or different alkyl group, aralkyl group, cycloalkyl group, carbocyclic or heterocyclic aromatic group, and R ₁ and R ₂ represent a hydrogen atom or a substituent that does not impart water solubility. A and B are the same or different compounds having a group represented by the following formula (2).

[0012]

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In the above formula (2), the substituents X, Y and Z are hydrogen, halogen, trifluoromethyl, cyano, alkyl having 1 to 12 carbons, 1 to 12 carbons. An 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. 6 represents a phenoxy group, a phenylmercapto group or a phenoxycarbonyl group substituted by an alkoxy group, and the substituents X, Y and Z may be different or the same;
And at least one of Z represents a hydrogen atom.

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

A and B as aralkyl groups are preferably straight-chain or branched and have 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. It may contain a monocyclic or tricyclic aryl group having an alkenyl group, most preferably a monocyclic or bicyclic aryl group. Examples of such aralkyl groups include benzyl and phenylethyl. A and B as the aromatic group are preferably a monocyclic to tetracyclic group, more preferably a monocyclic or bicyclic group, for example, a phenyl group, a diphenyl group or a naphthyl group. . A and B as the heterocyclic aromatic group are preferably a monocyclic or tricyclic group. These groups can be pure heterocyclic groups or those containing one or more fused benzene rings with a heterocyclic group, such as 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 Group,
Isoxazole group, thiazolyl group, indazolyl group, benzothiazolyl group, pyridazodinyl group, cinnolyl group,
Quinazolyl group, quinoxalyl group, phthalazinyl group, phthalazinionyl group, phthalimidyl group, chromonyl group,
Naphthactamyl group, benzopyridonyl group, maleimidyl group, naphthalidinyl group, benzimidazolonyl group, benzooxazolonyl group, benzothiazolonyl group, quinazolonyl group, pyrimidyl group, quinoxalonyl group, phthalozonyl group, dioxapyrimidinyl group, pyridonyl Group, isochirononyl group, isoquinolinyl group, benzisoxazolyl group, benzisothiazolyl group, indazolonyl group, acridinyl group, acrylonyl group, quinazolindionyl group, quinoxalindionyl group, benzoxatindionyl group and 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 non-water-soluble substituents are, for example, straight-chain or branched saturated or unsaturated carbon atoms having 1 to 18 carbon atoms.
And more preferably an alkyl group having 1 to 12 carbon atoms. 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. Such groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methylbutyl, n-heptyl, n-octyl, nonyl Group, decyl group, undecyl group, dodecyl group,
Examples include a stearyl group, a hydroxymethyl group, a trifluoromethyl group, a trifluoroethyl group, a cyanoethyl group, a methoxycarbonylmethyl group, and an acetoxymethyl group. Further, R ₁ and R ₂ may be an aryl group, preferably an unsubstituted or halogen atom, an alkyl group having 1 to 12 carbon atoms, and a C ₁ to 1 carbon atom.
Particularly preferred are compounds having 2 alkoxy groups, a phenyl group substituted by an alkylmercapto group having 1 to 12 carbon atoms, a trifluoromethyl group or a nitro group, wherein R ₁ and R ₂ are hydrogen atoms.

Further, preferred compounds are those wherein A and B are the same or different and have a group represented by the formula (2). Particularly preferred compounds are those wherein A and B in the formula (3) are such that _one of X ₁ and Y ₁ is a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, a cyano group, an N, H-dimethylamino group, an N, H -A diethylamino group, a C1 to C12 alkoxy group, a C1 to C12
Is an alkylmercapto group or an alkoxycarbonyl group having 2 to 4 carbon atoms, and the other substituent is a compound of (1) which represents a hydrogen atom. X ₁ and Y ₁ are located in the ortho, meta, and para positions with respect to the dithioketopyrrolopyrrole group, and are preferably located in the meta or para position.

[0018]

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The above-mentioned charge generating agent for 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 per 1 part by weight of the charge generating agent.
It is desirable to use them in parts by weight. The charge generation layer has a thickness of 0.01 to 1 μm, preferably 0.1 to 0.3 μm after drying. These charge generating substances can 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 uniformity of the film is excellent. For example, after the film is formed with the pyrrolopyrrole-based pigment or the phthalocyanine-based pigment, the film can be exposed to a solvent atmosphere such as toluene or xylene. Similar changes can be made in the solvent. The film thickness is 0.1-1 μm, preferably 0.1-0.5 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 good transport properties of the charge generated by the charge generating material, and is composed of an enamine-based hole. It is necessary to use a substance with good transportability.

[0021]

As the binder resin, those similar to the binder resin in the above-described charge generation layer can be used, and preferably, a polycarbonate resin, a styrene resin,
It is a styrene-butadiene copolymer resin. The binder resin is used in an amount of 0 to 10 parts by weight based on 1 part by weight of the charge transporting agent.
Preferably, it is used in a ratio of 0.1 to 1 part by weight. The thickness of the charge transport layer after drying is 1 to 50 μm, and preferably 10 to 30 μm.

The charge generating layer or the charge transporting layer may be added with a photo-sustained conductivity imparting agent, if necessary. Although the above-described charge generation layer and charge transport layer have photopersistence conductivity by themselves, this persistent conductivity imparting agent is added for the purpose of enhancing the photopersistence conductivity in the charge generation layer and charge transport layer. Things. Examples of such a photo-sustained conductivity imparting agent include arylmethane dyes, diazonium salts, acid anhydrides, o-benzosulfonimides, ninhydrins, cyano compounds, and the like as described in Japanese Patent Application No. 5-4721. Examples include nitro compounds, sulfonyl chlorides, diphenyl or triphenylmethanes, o-benzoyl benzoic acid, and leuco dyes. These photopersistence imparting agents are used in an amount of 0.001 to 1 part by weight, preferably 0.001 to 0.1 part by weight, per part by weight of the charge generating substance.
It is added in parts by weight. If the added amount of the photopersisting conductivity-imparting agent exceeds 1 part by weight, the photoconductive function as an optical sensor is remarkably deteriorated, which is not preferable.

Some of the above-mentioned light-sustained conductivity imparting substances have spectral sensitivities not in the visible light range. When light information in the visible light range is used, it is necessary to provide sensitivity in the visible light range. 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 a triphenylmethane dye, a pyrylium salt dye, and a xanthene dye. The electron-accepting substance, the sensitizing dye and the like are added at a ratio of 0.001 to 1 part by weight, preferably 0.01 to 1 part by weight, based on 1 part by weight of the charge generating substance. At the same time, if the optical information is in the infrared region, it is advisable to add the same amount of a pigment such as phthalocyanine, a pyrrole-based dye, or a cyanine-based dye, and conversely, there is information light in the ultraviolet region or in a wavelength region lower than that. in case of,
The purpose is achieved by adding the same amount of each wavelength absorbing substance.

In order to form a charge generation layer comprising an organic compound, dichloroethane, 1,1,2-trichloroethane, chlorobenzene, tetrahydrofuran,
The coating solution is preferably prepared using cyclohexanone, dioxane, 1,2,3-trichloropropane, ethyl cellosolve, 1,1,1-trichloroethane, dichloromethane, methyl ethyl ketone, chloroform, toluene, etc. The coating method is blade coating. Method, dipping method, spinner coating method and the like.

In the sensor of the present invention, a charge injection control layer may be formed between the electrode and the charge generation layer. The charge injection control layer is provided for controlling the charge injection property from the electrode layer 13 to the charge generation layer 14 'in the optical sensor 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 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 part and the potential (dark potential) applied to the information recording medium in the unexposed part is determined by 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 optical sensor needs to be set to about the operation start potential of the liquid crystal. For this purpose, the optical sensor bulk is required to have a conductivity such that a dark current of 10 ^-4 to 10 ^-8 A / cm ² is generated when an electric field of 10 ⁵ V / cm to 10 ⁶ V / cm ² is applied. Is 10 ^-5 to 10 ^-6 A
/ Cm ² is preferred. Dark current is 10 ^-8 A / cm ²
In the following optical sensors, the liquid crystal layer does not align even in the exposed state,
Further, in an optical sensor having a dark current of 10 ⁻⁴ A / cm ² or more, a large amount of current flows at the same time as 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 such characteristics of the information recording medium.

The electrode layer 13 needs 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. ^A material that stably gives a surface resistivity of ⁴ Ω / cm ² , for example, a metal thin film conductive film of zinc, titanium, copper, iron, tin, etc., tin oxide, indium oxide, zinc oxide, titanium oxide, tungsten oxide, vanadium oxide And an organic conductive film such as a quaternary ammonium salt, and may be 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. Further, the film thickness needs to be changed depending on the electric characteristics of the material constituting the electrode and the applied voltage at the time of information recording. For example, an ITO film has a thickness of about 10 to 300 nm, 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, but may be transparent or opaque if the information recording medium has transparency. It has a shape of a tape, a disk, or the like, 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, 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, if necessary. It is preferable to provide an antireflection property 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, the optical sensor 1 described above, Are arranged facing each other with a space provided between the optical sensor and the information recording medium, 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 a polymer-dispersed liquid crystal. The polymer-dispersed liquid crystal in the present invention has a structure in which synthetic resin particles are dispersed in a liquid crystal phase. As the 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 a memory property that maintains the orientation and permanently retains information. As a smectic liquid crystal, a liquid crystal material exhibiting a smectic A phase, such as a cyanobiphenyl-based, cyanoterphenyl-based, phenylester-based, or fluorine-based, having a long carbon chain at a terminal group of a substance exhibiting liquid crystallinity, is used as a ferroelectric liquid crystal. Liquid crystal material exhibiting a smectic C phase or a liquid crystal material exhibiting smectic H, G, E, F or the like.

A nematic liquid crystal may be used, and the memory property can be improved by mixing with a smectic or cholesteric liquid crystal. For example, Schiff base type, azoxy type, azo type, phenyl benzoate type, Cyclohexylic acid phenyl ester type, biphenyl type, terphenyl type, phenylcyclohexane type,
Known nematic liquid crystals such as phenylpyridine, phenyloxazine, polycyclic ethane, phenylcyclohexene, cyclohexylpyrimidine, phenyl and tolane can be used. Further, a mixture obtained by mixing a polyvinyl alcohol or the like with a liquid crystal material to form a microcapsule can also be used. When a liquid crystal material is selected, a material having a different direction of the refractive index is preferable because contrast can be obtained.

The material for forming the resin particles is, for example, an ultraviolet curable resin which is compatible with the liquid crystal material in the form of a monomer or an oligomer, or a solvent which is common to the liquid crystal material in the form of a monomer or an oligomer. The one having compatibility with is preferably used. Examples of such UV-curable resins include acrylic acid esters and methacrylic acid esters. In the form of monomers and oligomers, for example, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, polypropylene glycol Polyfunctional monomers such as diacrylate, isocyanuric acid (ethylene oxide-modified) triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, etc. or polyfunctional urethanes, esters Oligomer, nonylphenol-modified acrylate, N-vinyl-2-pyrrolidone, 2-hydroxy-3-phenoxy Monofunctional monomers or oligomers such as acrylate and the like. As the solvent, there is no particular problem as long as it is a common solvent, for example, a hydrocarbon solvent represented by xylene, a halogenated hydrocarbon solvent represented by chloroform, an alcohol derivative represented by methyl cellosolve, etc. Examples of the solvent include ether solvents such as a solvent and dioxane.

As a photo-curing agent for curing the ultraviolet curable resin, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 11 manufactured by Merck)
73), 1-hydroxycyclohexylphenyl ketone (Irgacure 184 manufactured by Ciba-Geigy), 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one (Darocure 1 manufactured by Merck)
116), benzyl dimethyl ketal (Irgacure 651 manufactured by Ciba-Geigy), 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropanone-1 (Irgacure 907 manufactured by Ciba-Geigy),
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.); Examples thereof include a mixture with ethyl p-dimethylaminobenzoate, and liquid 2-hydroxy-2-methyl-1-phenylpropan-1-one is compatible with a liquid crystal material, a polymer-forming monomer or oligomer. It is particularly preferred in terms of

The proportion of the liquid crystal material and the resin used is such that the content of the liquid crystal is 10% by weight to 90% by weight, preferably 40% by weight
The amount is preferably 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, phenomena such as oozing of the liquid crystal may occur. This causes image unevenness, which is not preferable. When a large amount of liquid crystal exists in the information recording phase, the contrast ratio can be improved and the operating voltage can be reduced.

The information recording layer is formed by applying a mixed solution in which a resin-forming material and a liquid crystal, a photo-curing agent or the like are dissolved or dispersed in a solvent onto the electrode layer using a blade coater, a roll coater, a spin coater, or the like. Apply by method,
It is formed by curing a resin forming material by light or heat. If necessary, a leveling agent may be added to improve the applicability of the solution and improve the surface properties.

In forming the information recording layer, the mixed solution of the resin forming material and the liquid crystal is heated to a temperature higher than the temperature at which the liquid mixture maintains an isotropic phase, and the liquid crystal and the ultraviolet curable resin forming material are completely compatible with each other. Therefore, an information recording layer in which the resin phase and the liquid crystal phase are uniformly dispersed can be obtained. When ultraviolet curing is performed at a temperature lower than the temperature at which the liquid crystal exhibits an isotropic phase, there is a problem that the phase separation between the liquid crystal and the ultraviolet-curable resin material is increased. That is, the liquid crystal domain grows too much, the skin layer is not completely formed on the surface of the information recording layer, and the liquid crystal oozes out, or the ultraviolet curable resin is matted, making it difficult to accurately capture information. Undesirably, 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 evaporating the solvent, if heating is required to maintain the isotropic phase, the wettability to the electrode layer is reduced,
There is a problem that a uniform information recording layer cannot be obtained.

For the purpose of maintaining wettability to the electrode layer and forming a film on the surface of the resin, a fluorine-based surfactant may be added to the information recording layer. Such fluorine-based surfactants include, for example, Florad FC-430 and Florad 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), par Fluorocaprylic acid (EF-2 manufactured by Mitsubishi Materials Corporation)
01), N- (n-propyl) -N-perfluorooctanesulfonic acid amide ethanol (EF-121 manufactured by Mitsubishi Materials Corporation), and EF-102, EF-103, and EF manufactured by Mitsubishi Materials Corporation -104, E
F-105, EF-112, EF-121, EF
-122A, EF-122B, EF-122C, EF-122A3, EF-123A, EF-123
B, EF-132, EF-301, EF-30
3, EF-305, EF-306A, EF-50
1, EF-700, EF-201, EF-20
4, EF-351, EF-352, EF-80
1, EF-802, EF-125DS, EF-1
200, EF-L102, EF-L155, EF
-L174 and EF-L215. Also,
3- (2-perfluorohexyl) ethoxy-1,2-
Dihydroxypropane (Mitsubishi Materials Corporation MF-
100), Nn-propyl-N-2,3-dihydroxypropyl perfluorooctylsulfonamide (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-120 manufactured by Mitsubishi Materials Corporation)
130), perfluorohexyl ethylene (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 Corporation)
160). The fluorine-based surfactant is added at a ratio of 0.1 to 20% by weight based on the total amount of the liquid crystal and the resin-forming material.

The solid content concentration in the coating solution for forming the information recording layer is preferably 10 to 60% by weight. In curing, the curing conditions such as the type and concentration of the resin, the temperature of the coating layer, and the conditions for irradiation with ultraviolet rays are appropriately adjusted. By setting
A skin layer composed of only a resin layer having no liquid crystal phase as an outer skin layer can be favorably formed, whereby the use ratio of liquid crystal in the information recording layer can be increased,
In addition, bleeding of the liquid crystal can be eliminated. As described above, the UV-curable resin has been described as the resin material, but in addition, a solvent-soluble thermosetting resin having compatibility with a common solvent with the liquid crystal material, such as an acrylic resin, a methacrylic resin, a polyester resin, a polystyrene resin, Alternatively, a copolymer containing these as a main component, an epoxy resin, a silicone resin, or the like may be used. Since the thickness of the information recording layer affects the resolution, the 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.

In the case where 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 when laminated by a method or the like, cracks do not occur and conductivity can be prevented from lowering. In this case, after providing the electrode layer on the information recording layer provided on the temporary support, the temporary support may be peeled off to obtain an information recording medium.

The electrode layer 13 'in the information recording medium is provided on the substrate 15 using the same material and the same laminating method as the electrode layer 13 in the above-described optical sensor. As shown in FIG. 2, this information recording medium is disposed opposite to the above-mentioned optical sensor via a spacer 19, and the two electrode layers 13, 1
3 'is connected via a voltage source V to form a first information recording system. Electrode layers 13, 13 'in this system
May be any one or both as long as they are 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,
A metal material such as selenium, tellurium, gold, or platinum or an inorganic or organic compound may be formed by evaporation. The thickness of the spacer is the gap distance between the optical sensor and the information recording medium,
Since this affects the distribution of the voltage applied to the information recording layer,
The thickness should be at least 100 μm or less, preferably 3 μm.
It is good to set it to μm to 30 μm.

Next, the second information recording system will be described. FIG. 3 is a diagram showing a second information recording system of the present invention in a cross-sectional view, 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 to face each other with the dielectric layer 20 interposed therebetween, and are directly laminated. The second information recording system is particularly suitable when the photoconductive layer in the optical sensor is formed by using a solvent, and when the information recording layer is directly formed on the photoconductive layer by their interaction, The liquid crystal in the information recording layer elutes, and the unevenness of the image due to the elution of the photoconductive material by the solvent for forming the information recording layer can be prevented, and the optical sensor and the information recording medium can be integrated. It is assumed that.

In forming the dielectric layer 20, it is necessary that the dielectric layer 20 does not have solubility in any of the photoconductive layer forming material and the information recording layer forming material, and that it does not have conductivity. It 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, since the dielectric layer lowers the distribution voltage applied to the liquid crystal layer or deteriorates the resolution, it is preferable that the film thickness is thinner, and it is preferable that the film thickness be 2 μm or less. In addition to the occurrence of image noise due to the interaction, there is a problem of penetration due to defects such as pinholes during the layer coating. Since the permeability due to defects such as pinholes differs depending on the solid content ratio of the material to be laminated and the type of solvent and the viscosity, the film thickness of the material to be laminated is appropriately set, but at least 10 μm.
The thickness is preferably as follows, and more preferably, 0.1 to 3 μm. Further, in consideration of the voltage distribution applied to each layer, a material having a high dielectric constant as well as a thin film is preferable.

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
, TiN or the like, and may be formed by laminating by a vapor deposition method, a sputtering method, a chemical vapor deposition (CVD) method, or the like. Also,
Using an aqueous solution of a water-soluble resin having low compatibility with an organic solvent, for example, polyvinyl alcohol, aqueous polyurethane, water glass, etc., a spin coating method, a blade coating method,
You may laminate | stack by a roll coating method etc. Further, a fluorine resin which can be applied may be used. In this case, the resin may be dissolved in a fluorine-based solvent and applied by a spin coating method, or may be laminated by a blade coating method, a roll coating method or the like. Examples of the fluorine resin which can be applied include, for example, JP-A-1-1
An organic material such as polyparaxylylene, which can be formed into a film by a vacuum system, and a fluorine resin disclosed in Japanese Patent No. 31215 or the like can be preferably used.

The outline of the information recording system according to the present invention has been described above. Here, the operation of amplifying the photocurrent in the optical sensor will be described. The measuring light sensor, ITO electrode layer is provided on a transparent glass substrate, an optical sensor photoconductive layer is formed by stacking on the electrode layer, 0.16 cm ² on the photoconductive layer, A gold electrode layer having a thickness of 10 nm and a surface resistance of 1 kΩ / □ is formed by lamination. Then, a constant DC voltage is applied between the two electrodes, and light is irradiated from the substrate side for 0.033 seconds after 0.5 seconds from the start of voltage application, and the current value behavior of the optical sensor during the measurement time is measured by light irradiation. Measure from the start (t = 0). Irradiation light was selected from a xenon lamp (L2274 manufactured by Hamamatsu Photonics) and a green filter (manufactured by Nippon Vacuum Optics) to select and irradiate green light.
The irradiation light intensity was measured with an illuminometer (manufactured by Minolta), and the intensity was set to 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 enter the photoconductive layer. When all the incident photons are converted into optical carriers, a photocurrent of 1.35 × 10 ⁻⁶ A / cm ² per unit area is theoretically generated.

Here, when the measurement is performed by the above measurement system, the ratio of the photo-induced current actually generated by the optical sensor to the theoretical photo-current (photo-induced current value actually generated by the optical sensor / theoretical value) Photocurrent value) is defined as the quantum efficiency of the optical sensor. The photo-induced current is the value obtained by subtracting the dark current value from the current value of the light irradiating part. Good, different from so-called photocurrent. The photocurrent amplification action in the photosensor of the present invention is defined as such a behavior of the photoinduced current.

An optical sensor having a photocurrent amplifying action and an optical sensor not having a photocurrent 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 above-mentioned measuring system. First, the measurement results of the comparative sensor are shown in FIG. In FIG. 5, the line (m) is a reference line indicating the above theoretical value (1.35 × 10 ⁻⁶ A / cm ² ), in which the light irradiation was performed for 0.033 seconds, and the voltage application was continued after the light irradiation. Is shown. The line (n) is an actual measurement line of an optical sensor having no photocurrent amplifying action, and shows 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 ). The quantum efficiency of this comparative sensor is almost constant at 0.4. FIG. 6 shows a change in quantum efficiency during light irradiation. On the other hand, in the optical sensor of the present invention, the photocurrent increases during light irradiation as shown in FIG. 7, and as shown in FIG. Efficiency exceeds 1,
It can be seen that the quantum efficiency continues to increase thereafter.

In the comparative sensor, the photocurrent becomes zero at the same time as the end of the light irradiation, so that no current flows even if a voltage is continuously applied after the light irradiation. On the other hand, in the optical sensor of the present invention, by continuing the voltage application even after the light irradiation is completed, the photo-induced current flows continuously, and the photo-induced 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 per unit area in the theoretical optical sensor having a quantum efficiency of 1 is shown by a line (O), and the time change of the integrated value of the current per unit area in the comparative sensor is shown by a line (P). Show. The integrated value Q of the current in FIG. 9 is Q = ∫ (I _PHOTO −I _dark ) dt (C). From the figure, it can be seen that the comparison sensor
_{Since PHOTO- Idark} becomes zero, no increase in the integral value is observed. FIG. 10 similarly shows a 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 optical sensor having a quantum efficiency of 1 is shown by the line (O), and the time change of the integrated value of the current in the optical sensor of the present invention is shown by the line (P). Indicated by As shown in the figure, since the optical sensor of the present invention continues to increase even after the end of light irradiation, it can be seen that a great effect can be obtained as compared with the comparative sensor.

Next, an information recording method in the first and second information recording systems of the present invention will be described. FIG.
FIG. 3 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
Denotes an electrode layer of an optical sensor, 13 'denotes an electrode layer of an information recording medium, 14 denotes a photoconductive layer, 21 denotes a light source, 22 denotes a shutter having a driving mechanism, 23 denotes a pulse generator (power supply), and 24 denotes a dark box. When information light is incident from the light source 21 while applying a voltage between the electrode layers 13 and 13 ′ by the pulse generator 23, photocarriers generated in the photoconductive layer 14 in the portion where the light is incident are formed by both electrodes. The electric field moves to the interface on the information recording layer 11 side,
The voltage is redistributed, the liquid crystal phase in the information recording layer 11 is oriented, and recording according to the information light pattern is performed. In addition, since the operating voltage and the 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 determined by the operating voltage of the liquid crystal. It is good to set to the area.

According to the information recording method of the present invention, a planar analog recording is possible and a recording at a liquid crystal level can be obtained.
High-resolution recording is obtained, and the exposure pattern is kept visible by 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 by a camera, an information recording medium is used instead of a photographic film used in a normal camera, and a recording member is used, and an optical shutter may be used,
Also, an electric shutter can be used. Also,
Optical information is converted into R,
G and B light components are separated and extracted as parallel light.
One frame is formed by three information recording media for each color of B, or R, G,
By recording each image of B to make one frame, it is possible to perform color photographing.

As a recording method using a laser,
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,
Laser exposure corresponding to an image signal, a character signal, a code signal, and a line drawing signal is performed by scanning. Analog recording such as an image is performed by modulating the light intensity of a laser, and digital recording such as characters, codes, and line drawings is performed by ON-OFF control of a laser beam. In the case where halftone dots are formed in an image, the laser light is formed by performing dot generator ON-OFF control. Note that the spectral characteristics of the photoconductive layer in the optical sensor need not be panchromatic, but may be any as long as they have sensitivity to the wavelength of the laser light source.

As shown in FIG. 12, 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, and is left unchanged in the case of the second information recording system. When 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, whereas the light B is scattered in the portion where the information is not recorded, and the information recording portion is not scattered. Contrast can be obtained.
Further, reading may be performed by reflected light via a 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 reflection type such as aluminum, or a dielectric mirror layer may be provided between the electrode and the liquid crystal layer.
In the case of the second information recording medium, reflection reading becomes possible by using the dielectric layer as a dielectric mirror layer. The information recorded by the orientation of the liquid crystal is visible information that can be read visually, but it can also be read by enlarging it with a projector, and the information can be read with high precision using laser scanning or a CCD. . Note that scattered light can be prevented by using a schlieren optical system as needed. As described above, as the information recording medium, the recording by the information exposure is visualized by the orientation of the liquid crystal, but by selecting the combination of the liquid crystal and the resin,
The information once oriented and visualized is not erased, and a memory property can be imparted. Further, when the memory is heated to a high temperature near the isotropic phase transition, the memory can be erased, so that it can be used for information recording 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 form of electrostatic charge on an information recording medium, the electrostatic charge is developed with toner, or the electrostatic charge is transferred, for example, as disclosed in
As described in Japanese Patent No. 90366 and the like, reproduction can be performed by reading potential. Also, JP-A-4-4634
For example, an information recording medium having a thermoplastic resin layer as an information recording layer, which is described in JP-A-7-1995, may be used.
After the information is accumulated on the surface in the form of an electrostatic charge as described above, the thermoplastic resin layer is heated, whereby the information is accumulated as a frost image, and the information can be reproduced as visible information.

[0058]

According to the present invention, there is provided 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 in which information can be recorded 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 information recording on an information recording medium by recording information in a state in which a voltage is applied between both electrodes, the recording medium being opposed to the recording medium. Because I used
The amplification factor of the optical sensor increases, enabling high-sensitivity information recording.In addition, even when the light irradiation is terminated, the electric conductivity or the electric charge corresponding to the light irradiation amount is maintained when the voltage is continuously applied. Since it has a function of applying the above-described electric field or charge amount to the information recording medium, it is possible to record information with higher sensitivity.

[0059]

Embodiments of the present invention will be described below. Example 1 A film having a thickness of 1 mm was placed on a sufficiently cleaned glass substrate having a thickness of 1.1 mm.
A 00 nm ITO film was formed by sputtering to obtain an electrode layer. On the electrode, the following structure as a charge generating agent

[0060]

Embedded image

Is mixed with 1 part by weight of a polyvinyl butyral resin (BMS: Sekisui Chemical Co., Ltd.) and 120 parts by weight of 1,2-dichloroethane and dispersed with a paint shaker for 3 hours. And applied with a spinner at 3000 rpm for 0.4 seconds, and then dried at 100 ° C. for 1 hour to form a film having a thickness of 300 nm.
Were laminated. On the charge generation layer, a charge transport agent having the following structure

[0062]

Embedded image

3 parts by weight of an enamine derivative, 2 parts by weight of a polystyrene resin (HRM-3, manufactured by Denki Kagaku Kogyo KK)
A coating solution obtained by mixing 22 parts by weight of 1,1,2-trichloroethane and 14 parts by weight of dichloromethane was mixed with a spinner to obtain 4 parts.
An optical sensor according to the present invention having a 20 μm-thick photoconductive layer composed of a charge generating layer and a charge transporting layer after coating at 00 rpm for 0.4 second and drying at 80 ° C. for 2 hours to form a charge transporting layer. I got

(Electrical Characteristics of Optical Sensor) In order to measure the electrical characteristics of the optical sensor obtained above, a 300 nm thick, 0.16 cm area was formed on the charge transport layer of the optical sensor.
A current measuring system as shown in FIG. 13 was constructed by depositing a gold layer of No. ² to form a counter electrode and a measuring medium. In the figure, 15 is the substrate of the optical sensor, 13 is the electrode layer of the optical sensor, 14 is a photoconductive layer composed of a charge generating layer and a charge transport layer, 30 is a gold electrode, 31 is a light source, and 32 is a shutter (No. .
0 electromagnetic shutter), 33 is a shutter drive mechanism, 3
Reference numeral 4 denotes a pulse generator (Yokogawa Hewlett-Packard), and 35 denotes an oscilloscope (VC-6, Yokogawa Hewlett-Packard).

In this current measuring system, the electrode layer 13 of the optical sensor is positive, the gold electrode is
At the same time as applying a DC voltage of 00 V, 1/30 from the glass substrate side through R, G, and B filters, respectively.
Exposure for seconds. Exposure illuminance irradiates light of R, G, B of 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. Further, only voltage application was performed without exposure, and current was measured in the same manner. FIG. 15 shows the obtained result. The horizontal axis represents the voltage application time (second), and the vertical axis represents the current density (μA / cm ² ). According to the optical sensor of the present invention, the amount of current is reduced to two inflection points
(B) is observed. The amount of current below the inflection point (a) is
From comparison with the optical sensor described in Comparative Example 1 described below,
This 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. The inflection point (b) is a point at which the amount of current changes with the end of the exposure.
It can be seen that the photo-induced current flows continuously and gradually attenuates. That is, from this figure, the photosensor of the present invention shows that the photocurrent continues to increase during the exposure,
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 optical sensor for measurement and the condenser C _{1 were used.}
(160 pF), a resistor R ₁ (1000 MΩ), a power supply (E), and a voltmeter (V). The capacitors and resistors correspond to the information recording medium. At the same time when an external voltage is applied to this measuring circuit, light of 20 lux (wavelength: 550 nm) is 1/30 from the optical sensor side.
Exposure for seconds. Voltage application continued for 0.15 seconds. The applied voltage was set so that the potential of the unexposed portion became 200 V when the potential difference (ΔV) between the exposed portion and the unexposed portion became maximum. FIG. 16 shows the results. The maximum potential differences were 105 V, 123 V, and 100 V for R, G, and B, respectively. The applied voltage was 550 V and 80 msec.

Reference Example 1 A charge transporting agent having the following chemical structure

[0068]

Embedded image

An optical sensor was produced in the same manner as in Example 1 except that the compound was used, and the electrical characteristics of the optical sensor were produced in the same manner as in Example 1 using green light among R, G and B. 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 ms. Example 2 A charge transport agent having the following chemical structure

[0070]

Embedded image

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 manufactured in the same manner as in Example 1 using green light among R, G, and B. 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, and the applied voltage was 630 V for 100 ms.

Reference Example 2 A charge transporting agent having the following chemical structure

[0073]

Embedded image

An optical sensor was produced in the same manner as in Example 1 except that the compound was used, and the electrical characteristics of the optical sensor were produced in the same manner as in Example 1 using green light among R, G and B. 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, and the applied voltage was 450 V for 65 ms. Reference Example 3 A charge transporting agent having the following chemical structure

[0075]

Embedded image

An optical sensor was produced in the same manner as in Example 1 except that the compound was used, and the electrical characteristics of the optical sensor were produced in the same manner as in Example 1 using green light among R, G and B. And the results are shown in FIG. 20, and the information recording characteristics are shown in FIG. The maximum potential difference was 101 V, and the applied voltage was 450 V for 65 ms.

Reference Example 4 A charge transporting agent having the following chemical structure

[0078]

Embedded image

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 is shown. The maximum potential difference is 95 V, and the applied voltage is 44
0 V, 70 msec.

Example 3 A 10 mm-thick film was placed on a sufficiently cleaned 1.1 mm thick glass substrate.
A 0 nm ITO film was formed by sputtering to obtain an electrode. A pyrrolopyrrole-based pigment having the same structure as in Example 1 was 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 as in Example 1, and the results are shown in FIG.
In the imaging evaluation, a good printed matter was obtained.

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

[0082]

Embedded image

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

Comparative Example 2 A 1.1 mm thick glass substrate which had been sufficiently washed
A 00 nm ITO film was formed by sputtering to obtain an electrode layer. On the electrode, the following structure as a charge generating agent

[0085]

Embedded image

Is mixed with 3 parts by weight of a bisazo pigment having the above formula, 1 part by weight of polyvinyl butyral, 98 parts by weight of 1,4-dioxane and 98 parts by weight of cyclohexanone, and the mixture is dispersed by a paint shaker for 6 hours to obtain a coating solution. , 0.4 seconds, 100 ° C, 1
After drying for a time, a charge generation layer having a thickness of 300 nm was laminated. On the charge generation layer, a charge transport agent having the following structure

[0087]

Embedded image

A coating solution obtained by mixing 3 parts by weight of the above compound, 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 with a spinner at 400 rpm for 0.4 seconds. Later, 8
After drying at 0 ° C. for 2 hours, the charge transport layer was laminated to obtain a photosensor of the present invention having a 20 μm-thick photoconductive layer composed of 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 light of each color of R, G, and B was found to be amplified, the contrast current was smaller than that of the example, and the respective currents of R, G, and B were different from each other. As for the 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
V, G: 33.1V, B: 22.6V.

[0089]

According to the present invention, 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 on which information can be recorded by an electric field or electric charge are laminated on the electrode layer. The optical sensor in the information recording system to the information recording medium by the information recording in a state where a voltage is applied between both electrodes, containing a pyrrolopyrrole compound and a charge transport material Since a photoconductive layer containing an enamine derivative was used as
The amplification factor of the optical sensor increases, enabling high-sensitivity information recording.In addition, even when the light irradiation is terminated, the electric conductivity or electric charge corresponding to the light irradiation amount is maintained by continuously applying the voltage when the voltage is continuously applied. An optical sensor having a function of applying the above-described electric field or electric charge to an information recording medium enables highly sensitive information recording.

[Brief description of the drawings]

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

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

FIG. 3 is a cross-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 amplifying action of the optical sensor of the present invention.

FIG. 5 is a diagram illustrating a measurement result of a photocurrent amplifying action of a comparative sensor.

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

FIG. 7 is a diagram illustrating a photocurrent amplifying action in the optical sensor of the present invention.

FIG. 8 is a diagram showing a change in quantum efficiency during light irradiation of the optical sensor of the present invention.

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 time change of an integrated value (charge amount) of a current amount in the optical sensor of the present invention.

FIG. 11 is a diagram illustrating an information recording method according to 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 for explaining a measurement circuit used for evaluating the electrical characteristics of the optical sensor according to the present invention.

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

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

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

FIG. 17 is a view showing electric characteristics of a reference example 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 electric characteristics of a photosensor of a reference example in the present invention.

FIG. 21 is a diagram showing information recording characteristics of a reference example of the optical sensor of the present invention.

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

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

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

FIG. 25 is a diagram illustrating electrical characteristics of an optical sensor of a comparative example.

FIG. 26 is a diagram illustrating electrical characteristics of an optical sensor according to a comparative example.

FIG. 27 is a diagram illustrating information recording characteristics 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 a driving 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

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Minoru Utsumi 1-1-1 Ichigaya-Kaga-cho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (56) References JP-A-5-273581 (JP, A) JP-A-5-273577 (JP, A) JP-A-5-142813 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G02F 1/135 G02F 1/13 505 G03G 5/04 G02F 1/361

Claims (3)

(57) [Claims] 1. An optical sensor comprising an electrode layer provided on a substrate 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 laminated on the electrode layer. A photoconductive layer of an optical sensor used for an information recording system in which information is recorded on an information recording medium by exposing information in a state where a voltage is applied between both electrode layers. Contains a pyrrolopyrrole compound represented by the following chemical structural formula and also contains an enamine derivative as a charge transporting substance. Embedded image 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 comprising an electrode layer and a photoconductive layer laminated on a base material, the electric field strength or the amount of electric charge applied to the information recording medium is amplified with light irradiation, and even after the light irradiation is completed. 2. The optical sensor according to claim 1, wherein the optical sensor has a function of maintaining its conductivity when a voltage is continuously applied, and continuously applying an electric field intensity 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 also containing an enamine derivative as a charge transporting substance: 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 layer, is arranged to face each other, and the information recording medium is exposed to information by applying a voltage between both electrode layers. An information recording system capable of recording information. Embedded image 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. An information recording system capable of recording information on a body.