JPH087328A - Information recording medium - Google Patents

Abstract

PURPOSE:To record data with high quality without bringing about granular grittiness to the recorded data, by forming an ultraviolet-curing resin monomer of a information recording medium having information recording layer of a liquid crystal of an ultraviolet-curing resin separate type layered on an electrode, in a composition represented by a general formula. CONSTITUTION:A data recording layer 11 formed of a liquid crystal of an ultraviolet curing resin dispersion type is layered on an electrode layer 13 in an information recording medium 3. An ultraviolet curing resin monomer is acrylic ester of dipentaerythritol represented by the formula and mainly composed of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. Of all the components, dipentaerythritol pentaacrylate is contained 22-32mol.% and dipentaerythritol hexaacrylate is 35-45mol.%. In the formula, R1-R5 are a hydrogen atom or a -COCH=CH2 base.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an information recording medium capable of obtaining electrostatic information recorded by an exposure recording method when a voltage is applied as visible information, and particularly, there is no noise due to graininess (roughness) of recorded information. The present invention relates to an information recording medium capable of recording high quality information.

[0002]

2. Description of the Related Art An optical sensor in which a photoconductive layer is laminated on an electrode and an information recording medium in which an information recording layer made of polymer dispersed liquid crystal is laminated on an electrode are arranged facing each other on the optical axis. Information recording / reproduction in which exposure is performed while applying voltage between electrode layers, the liquid crystal layer is oriented by the electric field formed by the optical sensor to record information, and when reproducing information, it is reproduced as visible information by transmitted light or reflected light. The method was previously filed as Japanese Patent Application No. 4-3394, Japanese Patent Application No. 4-24580, Japanese Patent Application No. 4-24722, and Japanese Patent Application No. 5-266646. This information recording / reproducing method makes it possible to visualize recorded information without using a deflector.

The applicant of the present invention uses an ultraviolet curable resin as the resin for forming the information recording layer,
The inside of the information recording layer has a structure in which a liquid crystal phase and an ultraviolet curable resin phase are dispersed, and since the surface of the information recording layer is formed of only the resin layer, the phenomenon of liquid crystal bleeding does not occur and the optical sensor It is possible to perform noise-free recording in information recording using, and to perform ITO on the resin layer by sputtering.
The inventors have found that it is possible to directly form an electrode layer such as a film, and filed an application earlier.

However, when the information recording layer is formed by using a polyfunctional UV-curable resin monomer, the recorded information has a graininess of graininess, which causes noise when reproducing the information, which results in deterioration of the recorded information. It turns out that problems can arise.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to an improvement of an information recording medium using an ultraviolet-curable resin-dispersed liquid crystal, which enables high-quality information recording without graininess of recorded information. To provide a reliable information recording medium.

[0006]

The first information recording medium of the present invention is an information recording medium comprising an electrode and an information recording layer comprising an ultraviolet curable resin-dispersed liquid crystal laminated on the electrode. Is the general formula (1)

[0007]

[Chemical 7]

(In the formula, R _{1 to} R ₆ are hydrogen atoms or --CO
CH represents a CH ₂ group. ) Is an acrylic acid ester of dipentaerythritol, which comprises dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate as main components, and contains 22 to 32 mol% of dipentaerythritol pentaacrylate in all the components, and dipentaerythritol. Hexaacrylate is 35-45
It is characterized by being a ratio of mol%.

The second information recording medium of the present invention is an information recording medium in which an information recording layer comprising an ultraviolet curable resin-dispersed liquid crystal is laminated on an electrode, wherein the ultraviolet curable resin monomer is represented by the general formula (2).

[0010]

Embedded image

(Wherein R _{1 to} R ₆ are hydrogen atoms or --CO
CH represents a CH ₂ group. ) Is an acrylic acid ester of dipentaerythritol, wherein dipentaerythritol tetraacrylate and dipentaerythritol hexaacrylate are the main components, and dipentaerythritol tetraacrylate is 55 to 65 mol% in all the components. Hexaacrylate 18-28
It is characterized by being mol%.

Further, in the third information recording medium of the present invention, a photoconductive layer, an intermediate layer if necessary, an information recording layer made of a UV-curable resin-dispersed liquid crystal and an electrode layer are sequentially laminated on the electrode. In the information recording medium, the ultraviolet curable resin monomer is an acrylic acid ester of dipentaerythritol represented by the above general formula (1), and is composed mainly of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. 22 to 32 mol% of dipentaerythritol pentaacrylate,
Dipentaerythritol hexaacrylate is 35-4
It is characterized in that the proportion is 5 mol%.

Further, in the fourth information recording medium of the present invention, a photoconductive layer, an intermediate layer if necessary, an information recording layer made of a UV-curable resin-dispersed liquid crystal, and an electrode layer are sequentially laminated on the electrode. In the information recording medium, the ultraviolet curable resin monomer is an acrylic acid ester of dipentaerythritol represented by the above general formula (2), and is composed mainly of dipentaerythritol tetraacrylate and dipentaerythritol hexaacrylate. In the components, dipentaerythritol tetraacrylate is 55 to 65 mol%,
Dipentaerythritol hexaacrylate is 18-2
It is characterized by being 8 mol%.

Further, in the fifth information recording medium of the present invention, the intermediate layer in the above-mentioned third or fourth information recording medium is laminated on the photoconductive layer in the order of the insulating reflection layer and the transparent insulating layer. It is a thing.

FIG. 1A is a diagram for schematically explaining the cross sections of the first and second information recording media of the present invention.
Is an information recording medium, 11 is an information recording layer, 13 is an electrode layer, 1
Reference numeral 5 is a substrate.

The information recording layer 11 is composed of a liquid crystal phase and a resin phase, and the liquid crystal material is a smectic liquid crystal,
A nematic liquid crystal, a cholesteric liquid crystal, or a mixture thereof can be used, but it is preferable to use a smectic liquid crystal from the viewpoint of so-called memory property that retains the orientation of the liquid crystal 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 having a long carbon chain at an end group of a substance exhibiting liquid crystallinity, a fluorine type or the like, a ferroelectric substance A liquid crystal substance exhibiting a smectic C phase used as a liquid crystal,
Alternatively, a liquid crystal substance exhibiting smectic H, G, E, F or the like can be given. A nematic liquid crystal may be used, and the memory property can be improved by mixing with a smectic or cholesteric liquid crystal, and examples thereof include a Schiff base type, an azoxy type, an azo type, a benzoic acid phenyl ester type, and a phenyl cyclohexylate. Known nematic liquid crystals such as ester type, biphenyl type, terphenyl type, phenyl cyclohexane type, 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.

In the information recording medium of the present invention, an acrylic acid ester of dipentaerythritol which is an ultraviolet curable resin is used as a material for forming the resin phase. This type of acrylic acid of dipentaerythritol is used. The reaction product of the ester has a structural formula represented by the general formula (1) or the general formula (2) depending on the esterification conditions in the production of the hexaacrylate, and both are dipentaerythritol hexaacrylate ester (DPHA). ) And is not completely a hexaacrylate body. The commercially available DPHA is
Of R _{1 to} R _{6 in} the above general formulas (1) and (2), 3
Are -COCH = CH ₂ groups, the others are hydrogen atoms in triacrylate, 4 are -COCH = CH ₂ groups, the others are hydrogen atoms in tetraacrylate, and 5 are -COCH = CH ₂
A pentaacrylate group in which the other is a hydrogen atom,
Six of them are in the form of a mixture of hexaacrylates having -COCH = CH ₂ groups.

The inventors of the present invention, in the first information recording medium, use an acrylic acid ester of dipentaerythritol represented by the general formula (1) as the ultraviolet curable resin monomer forming the information recording layer, Dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are the main components, and dipentaerythritol pentaacrylate is 25 to 30 mol% and dipentaerythritol hexaacrylate is 35 to 45% in all components.
In the second information recording medium, the acrylic acid ester of dipentaerythritol represented by the general formula (2), which comprises dipentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, is used. As a main component, dipentaerythritol tetraacrylate is 55 to 65 mol% in all components,
Dipentaerythritol hexaacrylate is 18-2
If the content of 8 mol% is used, the detailed reason for this is unknown, but in any case, an information recording layer having no graininess (roughness) and no noise can be formed, and high quality information recording is possible. I found that it could be a medium.

Next, the common solvent for the liquid crystal and the UV curable resin monomer is a solvent having a relative evaporation rate of less than 2 with respect to -n-butyl acetate, and the liquid crystal, the UV curable resin forming material, the photocuring agent, It is necessary that a common solvent be used for each of the fluorine-based surfactants. "A solvent having a relative evaporation rate of less than 2 with respect to -n-butyl acetate" means
For example, Yuji Harazaki "Easy-to-understand coating technology" 2
17 to 221, published by Riko Shuppansha, the evaporation rate is the volatility at a constant temperature, And R is less than 2.

Solvents that can be used in the present invention include
Xylene (R = 0.76), cyclohexanone (R =
0.32) and the like having a relatively slow evaporation rate are preferable,
Further, halogenated hydrocarbon solvents such as chloroform, alcohol derivative solvents such as methyl cellosolve, and ether solvents such as dioxane are also included. In addition, specifically, methyl alcohol,
Denatured ethanol, isopropanol, n-propanol, sec-butanol, isobutanol, n-butanol, methylisobutylcarbinol, diisobutylcarbinol, hexylene glycol, acetic acid-sec-butanol, isobutyl acetate (98%), n-butyl acetate , Methylaluminum acetate, aluminum acetate (95% isomer mixture), ethyl lactate, methyloxitol, ethyloxitol, isopropyloxitol, methyloxitol acetate, ethyloxitol acetate, butyloxitol, methyldioxitol, ethyl Dioxitol, butyldioxitol, butyldioxitol acetate, methyl isobutyl ketone, ethyl amyl ketone, Pent-O-xone (ME-6K), methylcyclohexanone, di Sobuchiruketon, diacetone alcohol, isophorone, 1,4-dioxane, perchlorethylene, dichloropropane, 2-nitropropane,
Toluene, SBP100 / 140, rubber solvent, xylene, SBP140 / 165, SBP6, SBP11, S
hellsolA, white spirit (LAWS),
ShellsolE, ShellsolTD, White Spirit (115 ° F flash), ShellsolT,
Shellsol AB, Distilate, Sol
Vent300, ShellsolN, Shellso
lRA, ShellsolK, ShellsolR, S
olvent350 etc. can be mentioned.

As the photo-curing agent, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one (“Darocur 1173” manufactured by Ciba-Geigy), 1-
Hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Geigy), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (“Darocur 111 manufactured by Ciba Geigy”)
6 "), 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.),
Isopropyl thioxanthone (a mixture of "Kunta Cure ITX" manufactured by Ward Brekinsop Co., Ltd.) and ethyl p-dimethylaminobenzoate can be mentioned, but it is in a liquid form.
-Hydroxy-2-methyl-1-phenylpropane-1
-One is particularly preferable in terms of compatibility with the liquid crystal material, the polymer-forming monomer or the oligomer.

The content ratio of the liquid crystal to the total amount of the liquid crystal and the resin is 10% by weight to 90% by weight, preferably 40% by weight to 80% by weight. When the content of the liquid crystal is less than 10% by weight, the light transmittance is low even if the liquid crystal phase is oriented by the information recording, and when it exceeds 90% by weight, the phenomenon such as exudation of the liquid crystal occurs to cause image unevenness. Not preferable. Further, according to the present invention, since the outer surface of the information recording layer can be a skin layer made of a resin layer, the content of the liquid crystal can be increased to 40% by weight to 80% by weight, in particular. The information recording medium can have high sensitivity and high contrast, and the operating voltage can be lowered.

In the information recording layer, the optical refractive index of the liquid crystal phase and the optical refractive index of the resin phase are substantially the same, so that the information recording layer is opaque due to light scattering when no electric field is applied, and the liquid crystal when an electric field is applied. Since the phases are oriented and the information recording portion can be made transparent, the deflecting plate is not required for reproducing information, and the optical system for reading can be simplified.

In the present invention, a fluorine-containing surfactant is added for the purpose of forming a skin layer made of only a resin on the surface of the information recording layer together with the wettability to the electrode layer. Examples of such fluorine-based surfactants include Sumitomo 3M Ltd.'s Florard FC-430, Florard FC-431, N- (n-propyl) -N- (β-acryloxyethyl) -perfluoro. Octyl sulfonic acid amide [Mitsubishi Materials Corp. EF-125M], N
-(N-Propyl) -N- (β-methacryloxyethyl) -perfluorooctylsulfonic acid amide [EF-135M manufactured by Mitsubishi Materials Corporation], perfluorooctanesulfonic acid [EF-10 manufactured by Mitsubishi Materials Corporation]
1], perfluorocaprylic acid [Mitsubishi Materials Corporation
EF-201], N- (n-propyl) -N-perfluorooctanesulfonic acid amide ethanol [EF-121 manufactured by Mitsubishi Materials Corp.], and EF-102 and EF-103 manufactured by Mitsubishi Materials Corp. , The same EF-10
4, the same EF-105, the same EF-112, the same EF-12
1, the same EF-122A, the same EF-122B, the same EF-1
22C, EF-122A3, EF-123A, E
F-123B, same EF-132, same EF-301, same E
F-303, EF-305, EF-306A, E
F-501, EF-700, EF-201, EF
-204, EF-351, EF-352, EF-
801, EF-802, EF-125DS, EF
-1200, EF-L102, EF-L155, EF-L174, EF-L215 and the like. In addition, 3- (2-perfluorohexyl) ethoxy-1,
2-dihydroxy propane [M manufactured by Mitsubishi Materials Corporation]
F-100], Nn-propyl-N-2,3-dihydroxypropyl perfluorooctyl sulfonamide [MF-110 manufactured by Mitsubishi Materials Corporation], 3- (2-
Perfluorohexyl) ethoxy-1,2-epoxypropane [MF-120 manufactured by Mitsubishi Materials Corporation], N-
n-propyl-N-2,3-epoxypropyl perfluorooctyl sulfonamide [MF-130 manufactured by Mitsubishi Materials Corporation], 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 [M manufactured by Mitsubishi Materials Corporation]
F-160] and the like. The fluorine-based surfactant is 0.1 to 20% by weight based on the total amount of liquid crystal and resin forming material.
Used in proportion. Further, if necessary, a leveling agent may be added in order to improve the suitability for application of the solution and improve the surface property.

Next, as a method of forming the information recording layer, liquid crystal, an ultraviolet curable resin monomer, a photopolymerization initiator and a surfactant are mixed with a solvent having a relative evaporation rate of less than 2 with respect to -n-butyl acetate. , Solid content concentration of 10 to 60% by weight
And the mixed solution. Solvent dilution is 1 to 500 cps
(20 ° C), preferably 10 to 200 cps (20 ° C)
Is. If the viscosity is low, the coating solution will flow and the film thickness after coating cannot be maintained, and if the viscosity is high, leveling will be difficult. Further, the liquid crystal is heated to a temperature higher than the temperature at which the liquid crystal retains an isotropic phase, preferably within a temperature range of the isotropic phase transition point + 10 ° C. to dissolve the liquid crystal, and the mixed solution is spin-coated on the electrode layer under a room temperature condition or a bar coat. , Blade coater,
Alternatively, it is applied uniformly with a uniform film thickness by a coating method such as a roll coater.

Next, the dried coating layer is irradiated with ultraviolet rays using a UV lamp to be cured. When the coating layer is irradiated with ultraviolet rays, the infrared rays are shielded to 200 n.
An information recording layer excellent in phase separation between a liquid crystal phase and a resin phase can be obtained by using ultraviolet rays having a wavelength portion of m to 400 nm of 1% or more and irradiating with energy of 0.1 mJ / cm ² or more. .

When the information recording layer is formed in this way,
0.01% to 3% of the thickness of the information recording layer on the surface of the information recording layer
A skin layer having a film thickness of 0% is formed, and the inside of the information recording layer has a primary particle diameter of 0.03 μm to 0.
It can have a structure in which resin particles of 3 μm are filled, and a liquid crystal phase communicates between them. Further, when the ultraviolet curable resin monomer represented by the above general formulas (1) and (2) is used, the surface skin layer can have excellent durability. By forming a durable skin layer on the surface of the information recording layer, it is possible to increase the use ratio of liquid crystal in the information recording layer, and there is no seepage of liquid crystal on the surface of the information recording layer. Can be eliminated and a high quality image can be obtained.

If the phase separation between the liquid crystal phase and the resin phase is incomplete in the fine structure inside the information recording layer, there is a problem that the contrast cannot be obtained. Also,
When the phase separation is incomplete, the resistance of the information recording layer itself becomes low, and during the information recording by the action of the electric field by the electrostatic information using the optical sensor, the voltage is not effectively applied to the liquid crystal phase in the information recording layer. However, there is a problem that the liquid crystal drive becomes slow and the sensitivity is lowered. In addition, if the phase separation is incomplete, when the UV curable resin forming material is irradiated with a UV lamp containing infrared rays, unnecessary heating causes non-uniform shrinkage, which is a fatal homogeneous and homogeneous information as an information recording medium. It causes a serious problem that the recording layer cannot be formed.

The average film thickness of the information recording layer thus formed is 1 μm to 30 μm. If the film thickness is too thick, the operating voltage will be high, but generally it is better to make the film thickness thinner to increase the sensitivity and thicker to increase the contrast. In order to achieve excellent sensitivity and contrast ratio, the film thickness is preferably 3 μm to 2
The film thickness may be 0 μm, more preferably 5 μm to 10 μm. As a result, the operating voltage can be lowered while maintaining high contrast.

The thickness of the skin layer in the information recording layer can be set to 0.01% to 50% of the thickness of the information recording layer, but if it is too thin, liquid crystal oozes out and its surface will be described later. Even if the information is recorded by the optical sensor, it becomes noise. Therefore, it is preferable that the thickness of the skin layer is 0.01% to 30% of the thickness of the information recording layer. Although the detailed reason is not clear, the film thickness of the skin layer can be appropriately adjusted by the irradiation amount of ultraviolet rays, addition of a fluorine-based surfactant, and the like.

Further, in the information recording medium of the present invention,
The thickness of the information recording layer needs to be applied accurately and uniformly. However, by forming the information recording layer by the above method, the uniformity of the film thickness is as follows when the film thickness is 5 μm to 10 μm. The surface roughness Ra can be set to 200 Å or less, the contrast is not uneven, and the shading phenomenon does not occur at the time of recording information.

In general, in the case of this type of polymer-dispersed liquid crystal, it is considered that the resolution depends more on the domain size of the liquid crystal than on the film thickness, but the information recording of the present invention. When the resin has a large liquid crystal content such as a layer and the resin phase forms in a particle shape, the domain size of the liquid crystal is taken into consideration much like a polymer dispersed liquid crystal having a low normal liquid crystal content. Since there is no need, it is possible to easily provide an information recording medium with high sensitivity and high contrast ratio.

Further, by forming a skin layer on the surface of the information recording layer in the first and second information recording media of the present invention, it is possible to prevent the liquid crystal from seeping out. In order to further improve the temperature, a thermoplastic resin film, a thermosetting resin film, an ionizing radiation curable resin film such as an ultraviolet curable resin, or the like may be laminated on the information recording layer by a coating method.

Particularly preferable examples of the material for forming these resin layers include polyethylene terephthalate, polyethylene, polypropylene, ultraviolet ray and electron beam curable resins and the like, and a hard coat layer having a high surface hardness even when formed into a thin film. Therefore, the durability of the information recording medium can be improved. The thickness of the resin layer is 0.1 μm to 20 μm.
m, preferably 0.1 μm to 5 μm.
However, when the film thickness of the resin layer is large, the operating voltage applied to the liquid crystal phase at the time of information recording becomes low. Therefore, when the optical sensor described later is used as the information recording mode, the applied voltage is increased. There is a need to. By laminating such a resin layer, it is possible to further prevent the phenomenon of liquid crystal seepage from the surface of the information recording layer, increase the hardness of the surface of the information recording layer, and make it durable. By changing the film thickness, the voltage applied to the information recording layer can be controlled, so that the recordable exposure range can be controlled.

The electrode layer 13 is required to be transparent when reading the information recorded in the information recording layer with transmitted light, and the metal thin film conductive film has a specific resistance value of 10 ⁶ Ω · cm or less. Film, conductive film of inorganic metal oxide such as indium tin oxide,
It is an organic conductive film such as a quaternary ammonium salt. The electrode layer 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 recording information. For example, an ITO film has a thickness of about 100 to 3000 Å, and the entire surface between the information recording layer and Alternatively, it is formed according to the formation pattern of the information recording layer.

When the information recorded on the information recording layer is read by reflected light, the electrode layer may be made light-reflective or a light-reflecting layer may be laminated on the transparent electrode layer. In order to make the electrode layer light-reflecting, a metal electrode such as aluminum may be used. As the light reflecting layer, for example, a dielectric mirror layer can be cited, and it is preferable to provide it on one side or on both sides of the electrode layer.

The substrate 15 may be either transparent or opaque depending on whether information is read by transmitted light or reflected light. The information recording medium may have a shape such as a card, a film, a tape, a disc, etc., but the support strongly supports the information recording medium, and when the information recording layer has supportability, No need to provide. The material and thickness of the support are not particularly limited, and include, for example, a flexible plastic film or glass,
Rigid bodies such as plastic sheets and cards are used. Specifically, when the information recording medium has a flexible film, tape, disc, or card shape, a flexible plastic film is used, and when strength is required, a rigid sheet or glass. Inorganic materials and the like are used.

When reproducing information with transmitted light, whether a layer having an antireflection effect is laminated on the substrate as necessary, or whether the transparent substrate is adjusted to a film thickness capable of exhibiting the antireflection effect. The antireflection property may be imparted by further combining the two.

Next, the method of recording information on the first and second information recording media of the present invention will be described. The information is recorded by using a method such as an optical sensor, heat, laser, corona charging, but preferably, an optical sensor is used,
Information should be recorded.

The photosensor is formed by laminating an electrode layer and a photoconductive layer on a transparent substrate, and the photoconductive layer is a single layer system having a charge generating function and a charge transporting function corresponding to information light at the same time. And a laminated system in which a charge generation layer and a charge transport layer are sequentially laminated on an electrode 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. When present, the effect is significant.

The single-layer photoconductive layer is formed of an inorganic photoconductive substance or an organic photoconductive substance. Examples of the inorganic photoconductive substance include Se, Se—Te, ZnO, TiO ₂ , and S.
i, CdS, etc., for example, vapor deposition method, sputtering method, CVD
On the electrode layer by a method or the like alone or in a mixed system of 5 to 30 μ
m, preferably 20 to 30 μm. Further, the above-mentioned inorganic photoconductor as fine particles may be dispersed in an organic insulating resin such as a silicone resin, a polyester resin, a polycarbonate resin, a styrene-butadiene resin, a styrene resin, or a polyvinyl acetal resin to form a photoconductive layer, In this case, 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, of the photoconductive fine particles are dispersed in 1 part by weight of the resin.

The organic photoconductive substance includes a polymer photoconductive substance and a dispersion of a low molecular weight photoconductive substance in an insulating binder. As the polymer photoconductive substance, for example, polyvinylcarbazole (PVK), poly-N-ethylenically unsaturated group substitution containing allyl group or acryloxyalkyl group ethylenically unsaturated group instead of vinyl group in PVK There are carbazoles, poly-N-ethylenically unsaturated group-substituted phenothiazines such as poly-N-acrylphenothiazine and poly-N- (β-acryloxy) phenothiazine, and polyvinylpyrene. Above all, poly
N-ethylenically unsaturated group-substituted carbazoles, particularly polyvinylcarbazole, are preferably used.

Examples of the low molecular weight photoconductive substance include oxadiazoles substituted with an alkylaminophenyl group and the like, triphenylmethane derivatives, hydrazone derivatives, butadiene derivatives, stilbene derivatives and the like. 1 part by weight is 0.1 to 5 parts by weight, preferably 0.1 to 1 part by weight of an electrically insulating resin such as a silicone resin, a polyester resin, a polycarbonate resin, a styrene-butadiene copolymer resin, a styrene resin or a polyvinyl acetal resin. It may be dispersed in parts by weight to form a film-forming organic photoconductive substance. The film thickness of these organic photoconductive substances after drying is 5 to 30 μm, preferably 10 to 30 μm.
m on the electrode.

If desired, the organic photoconductive layer is added with a persistent conductivity imparting agent described in Japanese Patent Application No. 4-287983. The above-mentioned organic photoconductive layer itself has a persistent conductivity, and this persistent conductivity imparting agent is added for the purpose of enhancing the persistent conductivity in the above-mentioned organic photoconductive layer. The persistent conductivity imparting agent is 0.001 to 1 part by weight with respect to 1 part by weight of the organic photoconductive substance,
Preferably 0.001 to 0.1 part by weight is added. If the added amount of the persistent conductivity imparting agent exceeds 1 part by weight,
This is not preferable because the amplification function of the photoconductive layer is significantly reduced. In addition, some persistent conductivity imparting substances do not have a spectral sensitivity in visible light, and when utilizing optical information in the visible light region, an electron-accepting substance is added to increase sensitivity in the visible light region. A dye or 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. Electron-accepting substances, sensitizing dyes, etc.
It is added in an amount of 0.001 to 1 part by weight, preferably 0.01 to 1 part by weight, relative to 1 part by weight of the organic photoconductive 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 this case, the purpose is achieved by adding the same amount of each wavelength absorbing substance.

Next, the laminated photoconductive layer is formed by sequentially laminating the charge generation layer and the charge transport layer on the electrode, and includes an inorganic material photoconductive layer and an organic material photoconductive layer. The charge generation layer in the inorganic system is formed by depositing Se—Te, Si doped with sulfur, oxygen, or the like on the electrode by a vapor deposition method, a sputtering method, a CVD method, or the like to have a film thickness of 0.05 μm to 1 μm. Then, as a charge transport layer, Se, As is formed on the charge generation layer.
₂ Se ₃ , Si, Si doped with methane or the like may be similarly laminated to have a film thickness of 10 μm to 50 μm.

Next, the charge generating layer in the organic system comprises a charge generating substance and a binder.
Fluorenone azo pigments, monoazo pigments, bisazo pigments, pyrrole pigments, azulenium salt pigments, phthalocyanine pigments, polycyclic aromatic pigments, pyrylium salt pigments, triazo pigments, squarylium salt pigments, perylene pigments , Antoanthrone pigments, cyanine pigments, polycyclic quinone pigments, imidazole pigments and the like, and specific examples thereof include the charge generating substances described in Japanese Patent Application No. 4-287983.

Examples of the binder include silicone resin, styrene-butadiene copolymer resin, epoxy resin, acrylic resin, saturated or unsaturated polyester resin, PMMA resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate mixed resin and the like. For example, the charge generation material is formed by dispersing it in a binder. The charge generating agent is preferably a fluorenone azo pigment or a bisazo pigment, and the binder is preferably a polyester resin or a vinyl chloride-vinyl acetate mixed resin. It is desirable that the charge generating agent and the binder are used in a mixing ratio of 0.1 to 10 parts by weight, preferably 0.1 to 1 part by weight, relative to 1 part by weight of the charge generating agent. The charge generation layer has a thickness after drying of 0.01 to 1 μm, preferably 0.1 to 1 μm.
0.3 μm is preferable.

The charge transport layer comprises a charge transport material and a binder. The charge transport material is a material having a good transport property of the charge generated by the charge generation material, and for example, a hydrazone-based material,
Pyrazoline-based, PVK-based carbazole-based, oxazole-based, triazole-based, aromatic amine-based, amine-based, triphenylmethane-based, butadiene-based, stilbene-based, polycyclic aromatic compound-based, etc. It is necessary to. Preferred are butadiene-based and stilbene-based charge transfer agents, and specifically, Japanese Patent Application No. 4-
The charge transport material described in Japanese Patent No. 287983 can be used.

As the binder, the same binders as those mentioned above in the charge generation layer can be used, but polyvinyl acetal resin, styrene resin and styrene-butadiene copolymer resin are preferable. The binder is
It is desirable to use 0.1 to 10 parts by weight, preferably 0.1 to 1 part by weight, relative to 1 part by weight of the charge transport agent. The thickness of the charge transport layer after drying is 1 to 50 μm, preferably 10 to 30 μm.

Examples of combinations of these charge generating substances and charge transporting substances include a combination of fluorenone azo pigment (charge generating substance) and stilbene type charge transporting agent, bisazo type pigment (charge generating substance) and butadiene type, hydrazone type. The combination of the charge-transporting agents described above is preferable.

The continuous conductivity-imparting agent and the electron acceptor described in the section of the single-layer photoconductive layer are added to the charge generation layer and the charge transport layer in the laminated photoconductive layer in the same proportions. However, it is preferably added to the charge generation layer.

When the single-layer photoconductive layer or laminated photoconductive layer is an organic photoconductive layer, dichloroethane, 1,1,2-trichloroethane, monochlorobenzene, tetrahydrofuran, cyclohexane, dioxane, 1 , 2,3-trichloropropane, ethyl cellosolve, 1,1,1, -trichloroethane, methyl ethyl ketone, chloroform, toluene and the like may be used as a coating solution. The coating method may be a blade coating method, a dipping method, a spinner. A coating method and the like can be mentioned.

The photoconductive layer may be provided on the electrode via the charge injection control layer. The charge injection control layer is provided as needed, and is provided to control the charge injection property from the electrode to the photoconductive layer and adjust the voltage substantially applied to the information recording medium. However, in the information recording medium of the present invention, it is necessary to set the sensitivity of the photoconductive layer in the operating voltage region of the liquid crystal in the information recording layer. That is, the difference (contrast potential) between the potential (bright potential) applied to the information recording layer in the exposed portion and the potential (dark potential) applied to the information recording layer in the unexposed portion is made large in the liquid crystal operating region. Because it is necessary.

Therefore, for example, the dark potential applied to the liquid crystal layer in the unexposed portion of the photoconductive layer needs to be set to about the operation start potential of the liquid crystal, and 10 ⁵ V / cm to 10 ⁵ V / cm to the bulk of the photoconductive layer.
10 ^-4 to 10 ^-8 A under an electric field of ⁶ V / cm
The conductivity is required to the extent that a dark current of / cm ² is generated, and the range of 10 ^-5 to 10 ^-6 A / cm ² is preferable.
In the photoconductive layer having a dark current of 10 ^-8 A / cm ² or less, the liquid crystal layer is not aligned even in the exposed state, and in the photoconductive layer having a dark current of 10 ^-4 A / cm ² or more, the voltage is applied even in the unexposed state. At the same time, a large amount of current flows, the liquid crystal in the information recording layer is not aligned, and even if it is exposed, the difference in its transmittance cannot be obtained. The charge injection control layer is appropriately provided in relation to the characteristics of such an information recording medium. When it is necessary to keep the dark potential in the photoconductive layer low, the charge injection control layer is a layer having a charge injection preventing property. There are two types of charge injection prevention layers, a layer utilizing a so-called tunneling effect and a layer utilizing a rectifying effect, and the one described in Japanese Patent Application No. 4-287983 can be used.

In the optical sensor described in this publication, the electric field or the amount of electric charge applied to the information recording medium at the time of light irradiation is amplified as the light is irradiated, and when the voltage is continuously applied even after the light irradiation is completed, the It has the function of maintaining conductivity and continuously applying an electric field or an amount of charge to the information recording medium.

An information recording device incorporating an optical sensor is shown in FIG. In the figure, 1 is an optical sensor, 3 is an information recording medium, and 1
3, 13 'are electrode layers, 14 is a photoconductive layer, 11 is an information recording layer, 15 is a substrate, 19 is a spacer, 21 is a light source, 22
Is a shutter having a drive mechanism, 23 is a pulse generator (power supply), and 24 is a dark box.

First, a voltage is applied between the electrodes 13 and 13 'by a power source. When recording on the information recording medium, the information recording medium is heated by, for example, resistance heating (not shown) embedded in the support to heat the liquid crystal to a temperature at which the liquid crystal phase is exhibited. Can be improved.

When information light is made incident from the light source 21 while applying a voltage between the electrodes 13 and 13 'by the pulse generator 23, the photo carriers generated in the photoconductive layer 14 at the portion where the light is made incident are generated on both electrodes. The electric field generated by the above moves to the interface on the information recording layer 11 side to redistribute the voltage, the liquid crystal phase in the information recording layer 11 is aligned, and recording is performed according to the pattern of the information light. In the figure, the photoconductor side is the positive electrode and the information recording medium side is the negative electrode, but it goes without saying that the polarity is set according to the discharge characteristics of the optical sensor.

When setting the applied voltage, since some liquid crystal materials operate at a low voltage, the voltage distribution of the optical sensor, the air gap, and the information recording medium is appropriately set and applied to the information recording layer. The voltage should be set in its operating voltage range. Information recording by this optical sensor is possible as planar analog recording, and since the liquid crystal phase can be aligned at the electrostatic charge level,
A high resolution similar to that of silver salt photography can be obtained, and the exposure pattern is retained as a visible image due to the orientation of the liquid crystal phase.

As a method of inputting information to the first and second information recording media of the present invention, there are a camera method and a laser recording method. As a method using a camera, an information recording medium is used instead of a photographic film used in a normal camera, and it is used as a recording member, and an optical shutter can be used and an electric shutter can also be used. It is profitable. Further, the optical information is separated into R, G, and B light components by a prism and a color filter, and taken out as parallel light to form one frame with three sets of R, G, B decomposed information recording media, or on one plane. R, G,
Color images can also be taken by arranging the B images side by side to form 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.

As shown in FIG. 3, when the electrostatic information recorded on the information recording medium is reproduced by the transmitted light, the liquid crystal is oriented in the electric field direction in the information recording portion, so that the light A is transmitted. On the other hand, the light B is scattered at the portion where no information is recorded, and the contrast with the information recording portion can be obtained.
The information recorded by the orientation of the liquid crystal is visible information that can be visually read, but it can also be magnified and read by a projector, laser scanning, or CC.
Information can be read with high accuracy by reading using D, and scattered light can be prevented by using a Schlieren optical system as needed. Furthermore, as described above, it is possible to read by reflected light by making the electrode layer itself light reflective or by laminating a light reflective layer on the electrode layer.

Next, the third and fourth information recording media of the present invention will be described. The third and fourth information recording media are obtained by incorporating a photoconductive layer into each of the first and second information recording media, and do not require an optical sensor or the like at the time of information recording and record information by themselves. Is possible. FIG. 1B is a diagram for schematically explaining the cross section,
In the figure, 3 is an information recording medium, 11 is an information recording layer, 13, 1
3'is an electrode layer, 14 is a photoconductive layer, and 15 is a substrate.

Photoconductive layer 14 laminated on electrode 13 '
Is the same as the photoconductive layer in the above-described photosensor, and the information recording layer 11 described in the section of the first information recording medium is provided on the photoconductive layer as the first information recording medium. It is laminated in the same manner.

In the information recording layers of the third and fourth information recording media, it is possible to prevent the liquid crystal from seeping out from the surface of the information recording layer. Therefore, the electrode layer 13 is directly provided on the surface of the information recording layer. It can be formed by vapor deposition by a sputtering method, has a high insulating property, and can be used as an information recording layer having no noise when recording information. Further, the electrode layers 13 and 13 'can employ the same material and forming method as the electrode layers in the above-mentioned first and second information recording media, but when reading recorded information with transmitted light, When transparency is required and when reading with reflected light, either one of the electrode layers may be made to have light reflectivity, or a light reflecting layer such as a dielectric mirror layer may be laminated on any one of the electrode layers. . A substrate may be laminated on the electrode 13 on the information recording layer.

Next, in the third and fourth information recording media, the space between the photoconductive layer 14 and the information recording layer 11 is shown in FIG.
It is preferable to provide the intermediate layer 12 as shown in FIG. When the photoconductive layer of the intermediate layer 12 is an organic photosensitive layer formed by using a solvent, the liquid crystal in the information recording layer may be eluted by the interaction depending on the solvent, or the information recording layer may be a photoconductive layer. The photoconductive material is eluted by the solvent for forming the information recording layer at the time of coating and forming it on the surface, and image unevenness occurs.

As such an intermediate layer, inorganic materials such as SiO ₂ , TiO ₂ , CeO ₂ , Al ₂ O ₃ , GeO ₂ , Si ₃ N ₄ , AlN,
TiN, MgF ₂ , ZnS or the like may be used and laminated by vapor deposition, sputtering, chemical vapor deposition (CVD) or the like.

An aqueous solution of polyvinyl alcohol, water-based polyurethane, water glass or the like may be used as a water-soluble resin having a low compatibility with an organic solvent, and the layers may be laminated by a spin coating method, a blade coating method, a roll coating method or the like. Good. 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. As the coatable fluorine resin, the fluorine resin described in Japanese Patent Application No. 4-24722 can be preferably used.

Further, in the case of an organic material which is formed into a film in a vacuum system, there is no fear of dissolving the photoconductive layer during the film formation. Of these, polyethylene, polypropylene, poly (monochlorotrifluoroethylene), polytetrafluoroethylene, etc. can be used as the material for forming the film by the vapor deposition method.
As a material for forming a film by the CVD method, polyparaxylene specifically described in Japanese Patent Application No. 4-24722 can be used.

Among the various materials mentioned above, it is particularly preferable to use polyvinyl alcohol, and when a material having a saponification degree of 97% or more and a polymerization degree of 1500 or more is used, the formation of the information recording layer is excellent. Can be something.

In forming the intermediate layer, it is necessary that the intermediate layer is not compatible with either the organic photoconductive layer forming material or the information recording layer forming material. Insulation of 10 ⁷ Ωcm or more is required because diffusion occurs and resolution deteriorates. Also,
The intermediate layer is preferably thin because it lowers the distribution voltage applied to the liquid crystal layer or deteriorates the resolution, and is preferably 2 μm or less, preferably 0.1 μm to 1.5 μm.
If it is too thin, not only image noise will be generated due to interaction over time, but also a problem of penetration due to defects such as pinholes will occur during multilayer coating. Since the permeability varies depending on the solid content ratio of the material to be laminated and coated, the type of solvent, and the viscosity, the film thickness of the material to be laminated and coated may be appropriately set. The intermediate layer is required to be transparent, and 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. If the photoconductive layer is formed of an inorganic material and there is no interaction such as liquid crystal seepage with the information recording layer, it is not necessary to provide the intermediate layer.

An information recording method on the third and fourth information recording media will be described with reference to FIG. First, when the information light 18 is incident while a voltage is applied between the electrodes 13 and 13 ′ by the power source, the photo carriers generated in the photoconductive layer 14 in the portion where the light is incident move due to the electric field formed by both electrodes. Then, by redistribution of the voltage, the liquid crystal phase in the information recording layer is oriented, and recording according to the pattern of the information light 18 is performed. The voltage may be applied for a predetermined time while the information light 18 is being incident.

Since some liquid crystals have different operating voltages and ranges, 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 operation of the liquid crystal. It is recommended to set it in the voltage range.

This information recording method enables planar analog recording and obtains high resolution because recording can be performed at the liquid crystal particle level, and the exposure pattern is retained as a visible image due to the orientation of the liquid crystal phase. To be done. Further, as the information input method, the same method as the method using the camera and the method described with the laser described in the section of the first information recording medium can be used. Further, the recording method using a laser can be similarly performed. Further, the spectral characteristics of the photoconductive layer do not need to be panchromatic, and may be sensitive to the wavelength of the laser light source. The information recorded on the third and fourth information recording media is read from the information recording layer side in the same manner as in the case of the first and second information recording media shown in FIG. The same applies when reproducing with transmitted light and reading with reflected light.

Next, the fifth information recording medium of the present invention will be described. As shown in FIG. 1D, the fifth information recording medium includes an insulating light reflection layer 12 'and a transparent insulating layer 1 between the photoconductive layer and the information recording layer in the third and fourth information recording media.
2 ″ is provided, and the read information from the information recording layer side is made incident on the recorded information and the read information is read by the reflected light.

Examples of the insulating light reflection layer 12 'include a dielectric mirror layer and a light-shielding film having light reflectivity. Examples of the dielectric mirror layer include those having a film thickness of λ / 4 and formed of, for example, a combination of silicon dioxide and titanium dioxide, or zinc sulfide and magnesium fluoride. As the light-shielding film having light reflectivity, for example, aluminum oxide, which is an insulating material, and germanium, which is a light-shielding material, are vapor-deposited at a rate of 50Å /
Second, germanium is vapor-deposited at a rate of 20 Å / sec at the same time to give a film thickness of about 1 μm. The reading light from the information recording side can be reflected and the information can be reproduced from the information recording layer side.

The transparent insulating layer 12 "is the insulating light reflecting layer 1
When the information recording layer 11 is directly formed on the 2 ', there is a problem that the insulating light reflecting layer 12' is peeled off, and the peeling can be prevented and the information recording layer 11 can be formed favorably. It may be formed similarly to the intermediate layer 12 in the second information recording medium.

Insulating light reflecting layer 12 ', transparent insulating layer 12 "
Has a lower film thickness, because it lowers the distribution voltage applied to the liquid crystal layer or deteriorates the resolution like the above-mentioned intermediate layer.
It is good to set it as m-1 micrometer.

In the fifth information recording medium, when the information is read, the read light does not pass through the generally colored photoconductive layer, so that the reproduced information can be noise-free.

In each of the first to fifth information recording media of the present invention, a primer layer is provided between the respective layers such as the electrode layer, the light reflection layer or the light reflection prevention layer, and the substrate to improve the adhesion. May be provided.

The primer layer is selected in consideration of the respective materials of the electrode layer, the light reflection layer or the light reflection prevention layer, and the substrate, and is made of an ionizing radiation curable resin such as a thermoplastic resin, a thermosetting resin, or an ultraviolet curable resin. It may be formed by applying a resin, or in the case of a combination of an inorganic material and an organic material, a known silane coupling agent, an organotitanium compound, an organoaluminum compound or other organometallic compound may be used. Further, a primer layer may be provided between the electrode layer and the information recording layer, and the same material as described above can be used as the material thereof. In this case, the film thickness is 0.01 μm to 10 μm. Since the voltage applied to the information recording layer can be controlled by improving the adhesion and changing the film thickness, the recordable exposure range can be controlled.

Further, the first to fifth information recording media of the present invention are used by being cut in the layer width direction into an appropriate size according to the usage mode, and the information recording is made at the cut surface. The inside of the layer is exposed, and the liquid crystal phase exudes during storage. When this bleeding phenomenon occurs, a problem arises in that when information is recorded, accurate information cannot be recorded at the edge of the information recording medium. In order to prevent this, after cutting the information recording medium into an appropriate shape, a resin layer may be similarly laminated on the cut surface by the coating method or the laminating method to protect the cut surface.

The first to fifth information recording media of the present invention are for recording electrostatic information in a state where the electrostatic information is visualized by the orientation of the liquid crystal. Oriented and visualized information is not erased, and a memory property is provided. To erase the memory, it is preferable to heat it to a high temperature near the isotropic phase transition, and it can be used again for information recording.

[0085]

According to the first to fifth information recording media of the present invention, the ultraviolet-curable resin in the information recording layer is a pentacrylic acid ester of dipentaerythritol having a specific composition, thereby providing recorded information. It is possible to record high-quality information without graininess.

Further, in the third and fourth information recording media, since the liquid crystal seepage phenomenon does not occur on the surface of the information recording layer, an electrode layer can be provided on the surface by a sputtering method or the like. Since the phenomenon such as cracking can be prevented, the conductivity of the electrode layer is not lowered. In addition, there is no noise during information recording, and the information recording layer can have a high resistance. Further, since it has a photoconductive layer, it is not necessary to combine it with an optical sensor, and information can be recorded by itself.

The fifth information recording medium may be suitable for reading recorded information by reflected light. Hereinafter, examples will be described. In the examples, “parts” means parts by weight and “%” means% by weight. The composition (mol%) of the acrylic ester of dipentaerythritol used in the following examples is also shown. The compositions A, B, and C are acrylic acid esters of dipentaerythritol represented by the general formula (1), and the compositions (D) are acrylic acid esters of dipentaerythritol represented by the general formula (2). Also,
In the following composition, "other" indicates a monoester body, a diester body, non-esterified dipentaerythritol and the like.

[0088]

[Table 1]

[0089]

Example 1 An indium tin oxide (ITO) film having a film thickness of 1000 Å was formed on a thoroughly washed glass substrate having a thickness of 1.1 mm by a sputtering method to obtain an electrode layer. On the electrode: -Acrylate ester of dipentaerythritol with composition A)-10 parts-Photocuring initiator (2-hydroxy-2-methyl-1-phenylpropane-1-one, Ciba Geigy) Made: Brand name Darocur 1173) ··· 0.5 part · Smectic liquid crystal (BDH: S-6) · · 10 parts · Liquid crystal (BDH: BL-066) · · 1 part · Surfactant (Sumitomo 3M company: trade name Florard FC-430) ··· 0.2 parts of xylene (manufactured by Junsei Kagaku Co., Ltd., reagent grade) 22 parts was uniformly dissolved to apply a solution using a spin coater,
Immediately after holding this at 47 ° C. for 3 minutes, holding it under reduced pressure vacuum for 2 minutes and returning to atmospheric pressure, immediately after 1600 mJ / cm 2.
By irradiating UV light of ² , an information recording layer having a film thickness of 6 μm was formed.

Further, the cut surface of the obtained information recording layer was extracted with hot methanol to dry the liquid crystal, and dried, and then a scanning electron microscope (S-800, 100 manufactured by Hitachi, Ltd.).
The internal structure of the layer was observed to be 0.
It was found that the structure was covered with an ultraviolet curable resin having a thickness of 6 μm (10% of the film thickness), and the inside of the layer was filled with resin particles having a particle diameter of 0.1 μm.

(Production of optical sensor) -The following structure as a charge generating agent

[0092]

Embedded image

Using 3 parts of a fluorenone azo pigment (manufactured by Nippon Senshoku Co., Ltd.) having 1 part, a polyester resin (manufactured by Toyobo Co., Ltd., Byron 200) and 1,4-dioxane: cyclohexanone = 1: 1, A 100 g solution with a solid content of 2% was sufficiently dispersed with a paint shaker to form a coating solution, and an IT having a film thickness of 500 Å and a resistance value of 80 Ω / cm ²
It is applied to the ITO side of the glass substrate having the O film using a blade coater with a gap of 2 mils, and the temperature is 100 ° C.
After drying for an hour, a charge generation layer having a thickness of 0.3 μm was laminated.

On the charge generation layer, the following structure was used as a charge transport agent.

[0095]

Embedded image

25 parts of para-dimethylstilbene, 5 parts of polystyrene resin (HRM-3 manufactured by Denka), 1,
1,2-trichloroethane 102 parts, dichloromethane 6
8 parts of the coating solution is applied using a blade coater, dried at 80 ° C. for 2 hours, and a charge transport layer is laminated to form a photoconductive layer having a thickness of 20 μm and including a charge generation layer and a charge transport layer. Layers were applied to obtain a light sensor.

Next, the obtained optical sensor and the information recording medium of the present invention produced as described above are arranged so as to face each other with a PET film of 10 μm as a spacer, and incorporated in the recording apparatus of FIG. Is positive and the information recording medium side is negative, and a DC voltage of 750 V is applied. With a voltage applied, exposure was performed from the photosensor side for 0.1 second using a halogen lamp with an illuminance of 1000 lux as a light source, and a gray scale was photographed.

After the exposure was completed, the information recording medium was taken out, and a Nikon type film scanner (LS-3510AF) was used, a xenon lamp was used as a light source, and the information was transmitted with the wavelength light through a wavelength filter (357 nm). Was read and output by a sublimation printer, the standard deviation of the same density portion in the output image was 2.9, and a good image without graininess was obtained.

[0099]

Example 2 In Example 1, the acrylic acid ester of dipentaerythritol of composition A in the information recording medium was changed to that of composition D, and the holding condition of the coating liquid was 40.
An information recording medium was prepared in the same manner as in Example 1 except that the sample was kept at 3 ° C. for 3 minutes and then kept under reduced pressure for 2 minutes, and information was recorded in the same manner as in Example 1. The standard deviation of the same density portion in the output image was 3 It was 0.1, and a good image without graininess was obtained.

[0100]

Example 3 Fluorine-containing resin CYTOP (trade name; Asahi Glass) on the photoconductive layer in the optical sensor prepared in Example 1.
Co., Ltd., water absorption 0.01%, specific resistance 1 × 10 ¹⁸ Ω · c
m) perfluoro (2-butyltetrahydrofuran)
Dissolve in, and the 4.5% solution is 1500r with a spinner.
pm, apply for 20 seconds, dry at 80 ° C for 1 hr,
An intermediate layer (transparent insulating layer) having a film thickness of 1 μm was formed.

Next, on this transparent insulating layer: -Acrylate ester of dipentaerythritol having composition A-33 parts-Photocuring initiator (2-hydroxy-2-methyl-1-phenylpropane-1) -On, manufactured by Ciba-Geigy: trade name Darocur 1173) -1.7 parts-Smectic liquid crystal (BDH: S-6) -70 parts-Liquid crystal (BDH: BL-066)- 7 parts-Surfactant (Sumitomo 3M: trade name Florard FC-430)-1 part was uniformly dissolved in 112 parts of xylene (Junsei Kagaku Co., Ltd., reagent grade) using a spin coater. Coating, and immediately holding this at 50 ° C. for 5 minutes, then holding it for 2 minutes under reduced pressure vacuum and returning to atmospheric pressure, and then immediately applying 1000 mJ /
cm ² of UV light is irradiated to form an information recording layer having a film thickness of 6 μm, and an Au film having a film thickness of 500 Å is formed as an upper electrode on the information recording layer by an evaporation method. Two
The information recording medium of was produced.

This information recording medium, as shown in FIG.
The photoconductive layer side electrode is positive and the information recording layer side electrode is negative 60
A DC voltage of 0V was applied. Exposure with a halogen lamp having an illuminance of 1000 lux as a light source was performed for 0.1 seconds from the photoconductive layer side under voltage application, and a gray scale was photographed.

After completion of the exposure, a Nikon type film scanner (LS-3510AF) was used, a xenon lamp was used as a light source, and information was read by transmitted light with the wavelength light through a wavelength filter (500 nm). When output, the standard deviation of the same density portion in the output image was 3.2, and a good image without graininess was obtained.

[0104]

[Example 4] In Example 3, the acrylic acid ester of dipentaerythritol of composition A was replaced with that of composition D in the information recording layer, and the holding condition of the coating liquid was 43 ° C.
After holding for 5 minutes, an information recording medium was prepared in the same manner except that it was held under reduced pressure vacuum for 2 minutes, and information was recorded in the same manner. The standard deviation of the same density portion in the output image was 3.5. It had a good image without graininess.

[0105]

Example 5 5 parts of polyvinyl alcohol (AH-26 of Nippon Synthetic Chemical Industry Co., Ltd., saponification degree of 99.5 mol% or more, polymerization degree of 1500 or more) on the photoconductive layer of the optical sensor prepared in Example 1. Was applied to 95 parts of ion-exchanged water by a spin coating method, dried at 80 ° C. for 1 hour, and an intermediate layer (transparent insulating layer) having a film thickness of 1 μm was laminated.

Then, 6 is formed on this intermediate layer in the same manner as in Example 3.
An information recording layer having a thickness of μm was formed, and an Au film having a film thickness of 500 Å was formed as an upper electrode on the information recording layer by vapor deposition to prepare a second information recording medium of the present invention.

This information recording medium, as shown in FIG.
The photoconductive layer side electrode is positive and the information recording layer side electrode is negative 60
A DC voltage of 0V was applied. Exposure with a halogen lamp having an illuminance of 1000 lux as a light source was performed for 0.1 seconds from the photoconductive layer side under voltage application, and a gray scale was photographed.

After completion of the exposure, a Nikon type film scanner (LS-3510AF) was used, a xenon lamp was used as a light source, and the information was read by the transmitted light with the wavelength light through a wavelength filter (500 nm). Upon output, the standard deviation of the same density portion in the output image was 3.0, and a good image without graininess was obtained.

[0109]

Example 6 In Example 5, the acrylic acid ester of dipentaerythritol of composition A was replaced with that of composition D in the information recording layer, and the holding condition of the coating liquid was 43 ° C.
After holding for 5 minutes, an information recording medium was prepared in the same manner except that it was held under reduced pressure for 2 minutes, and information was recorded in the same manner. The standard deviation of the same density portion in the output image was 3.2. It had a good image without graininess.

[0110]

[Embodiment 7] Zinc sulfide and magnesium fluoride are deposited on the photoconductive layer of the optical sensor manufactured in Embodiment 1 to have a film thickness λ.
/ 4n (light wavelength read out at λ = 370 nm, n is the refractive index, zinc sulfide is 2.38, and magnesium fluoride is 1.38, so zinc sulfide is 39 nm, magnesium fluoride is 67 nm) Then, six layers were alternately laminated by the EB vapor deposition method, and finally zinc sulfide was laminated to a film thickness of λ / 2 to laminate the insulating light reflecting layer.

Then, 5 parts of polyvinyl alcohol (AH-26 of Nippon Synthetic Chemical Industry Co., Ltd., saponification degree of 99.5 mol% or more, polymerization degree of 1500 or more) was added to 95 parts of ion-exchanged water on the insulating light-reflecting layer. The dissolved solution was applied by a spin coating method, dried at 80 ° C. for 1 hour, and a transparent insulating layer having a film thickness of 1 μm was laminated.

Then, an information recording layer having a thickness of 6 μm was formed on the transparent insulating layer as in Example 3, and an Au film having a film thickness of 500 Å was formed as an upper electrode on the information recording layer by vapor deposition. A fifth information recording medium of the present invention was produced.

A DC voltage of 600 V was applied to this information recording medium with the photoconductive layer side electrode being positive and the information recording layer side electrode being negative. Illuminance of 1000 from the photoconductive layer side when voltage is applied
Exposure was carried out for 0.1 seconds using a Lux halogen lamp as a light source, and a gray scale was photographed.

After the exposure, a Nikon type film scanner (LS-3510AF) was used, a xenon lamp was used as a light source, and information was read by transmitted light with the wavelength light through a wavelength filter (357 nm). When output, the standard deviation of the same density portion in the output image was 3.5, and a good image without graininess was obtained.

[0115]

Example 8 In Example 7, as the information recording layer, the acrylic ester of dipentaerythritol of composition A was replaced by that of composition D, and the holding condition of the coating solution was 43 ° C., 5
After holding for 1 minute, an information recording medium was prepared in the same manner except that it was held under reduced pressure and vacuum for 2 minutes, and information was recorded in the same manner. The standard deviation of the same density portion in the output image was 3.3. It had a good image with no property.

[0116]

Example 9 An information recording medium was prepared in the same manner as in Example 1 except that the acrylic ester of dipentaerythritol of composition A in the information recording medium was changed to that of composition B as the information recording layer. When information was recorded in the same manner, the standard deviation of the same density portion in the output image was 3.6, and a good image without graininess was obtained.

[0117]

COMPARATIVE EXAMPLE 1 An information recording medium was prepared in the same manner as in Example 1 except that the acrylic ester of dipentaerythritol of composition A was replaced with that of composition C as the information recording layer in the information recording medium. When information was recorded on the printed image, the standard deviation of the same density portion in the output image was 6.2, and an image with a lot of graininess and conspicuous roughness was obtained.

[Brief description of drawings]

FIG. 1 is a schematic view showing a cross section of an information recording medium of the present invention, (a) is a first and second information recording medium,
(B) and (c) are both third and fourth information recording media, and (d)
Shows a cross section of the fifth information recording medium.

FIG. 2 is a schematic diagram of an information recording device using an optical sensor.

FIG. 3 is a diagram for explaining a method of reproducing recorded information on an information recording medium with transmitted light.

FIG. 4 is a diagram for explaining an information recording method on third to fifth information recording media.

[Explanation of symbols]

1 is an optical sensor, 3 is an information recording medium, 11 is an information recording layer, 12 is an intermediate layer, 12 'is an insulating light reflecting layer, 12 "is a transparent insulating layer, 13 and 13' are electrode layers, and 14 is photoconductive. layer,
Reference numeral 15 is a substrate, 18 is information light, 19 is a spacer, 21 is a light source, 22 is a shutter having a driving mechanism, 23 is a pulse generator (power supply), 24 is a dark box, A is transmitted light,
B is scattered light.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display G03G 15/00

Claims (7)

[Claims] 1. An information recording medium comprising an information recording layer comprising an ultraviolet curable resin-dispersed liquid crystal laminated on an electrode, wherein the ultraviolet curable resin monomer is represented by the general formula (1): (In the formula, R _{1 to} R ₆ represent a hydrogen atom or a —COCH═CH ₂ group.) An acrylic ester of dipentaerythritol, which is mainly composed of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. An information recording medium characterized in that dipentaerythritol pentaacrylate is 22 to 32 mol% and dipentaerythritol hexaacrylate is 35 to 45 mol% in all components. 2. An information recording medium comprising an information recording layer comprising an ultraviolet curable resin-dispersed liquid crystal laminated on an electrode, wherein the ultraviolet curable resin monomer is represented by the general formula (2): (In the formula, R _{1 to} R ₆ represent a hydrogen atom or a —COCH═CH ₂ group.) An acrylic acid ester of dipentaerythritol, which is mainly composed of dipentaerythritol tetraacrylate and dipentaerythritol hexaacrylate. An information recording medium, wherein the content of dipentaerythritol tetraacrylate is 55 to 65 mol% and that of dipentaerythritol hexaacrylate is 18 to 28 mol% in all components. 3. In an information recording medium in which a photoconductive layer, an information recording layer made of a UV-curable resin-dispersed liquid crystal, and an electrode layer are sequentially laminated on an electrode, the UV-curable resin monomer has the general formula (1): Chemical 3] (In the formula, R _{1 to} R ₆ represent a hydrogen atom or a —COCH═CH ₂ group.) An acrylic ester of dipentaerythritol, which is mainly composed of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. An information recording medium characterized in that dipentaerythritol pentaacrylate is 22 to 32 mol% and dipentaerythritol hexaacrylate is 35 to 45 mol% in all components. 4. In an information recording medium in which a photoconductive layer, an information recording layer made of a UV-curable resin-dispersed liquid crystal and an electrode layer are sequentially laminated on an electrode, the UV-curable resin monomer has the general formula (2): Chemical 4] (In the formula, R _{1 to} R ₆ represent a hydrogen atom or a —COCH═CH ₂ group.) An acrylic acid ester of dipentaerythritol, which is mainly composed of dipentaerythritol tetraacrylate and dipentaerythritol hexaacrylate. An information recording medium, wherein the content of dipentaerythritol tetraacrylate is 55 to 65 mol% and that of dipentaerythritol hexaacrylate is 18 to 28 mol% in all components. 5. In an information recording medium in which a photoconductive layer, an intermediate layer, an information recording layer made of a UV-curable resin-dispersed liquid crystal and an electrode layer are sequentially laminated on an electrode, the UV-curable resin monomer has the general formula ( 1) [Chemical 5] (In the formula, R _{1 to} R ₆ represent a hydrogen atom or a —COCH═CH ₂ group.) An acrylic ester of dipentaerythritol, which is mainly composed of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. An information recording medium characterized in that dipentaerythritol pentaacrylate is 22 to 32 mol% and dipentaerythritol hexaacrylate is 35 to 45 mol% in all components. 6. An information recording medium in which a photoconductive layer, an intermediate layer, an information recording layer made of a UV-curable resin-dispersed liquid crystal and an electrode layer are sequentially laminated on an electrode, wherein the UV-curable resin monomer is of the general formula ( 2) [Chemical formula 6] (In the formula, R _{1 to} R ₆ represent a hydrogen atom or a —COCH═CH ₂ group.) An acrylic acid ester of dipentaerythritol, which is mainly composed of dipentaerythritol tetraacrylate and dipentaerythritol hexaacrylate. An information recording medium, wherein the content of dipentaerythritol tetraacrylate is 55 to 65 mol% and that of dipentaerythritol hexaacrylate is 18 to 28 mol% in all components. 7. The information recording medium according to claim 5, wherein the intermediate layer is formed by laminating an insulating reflective layer and a transparent insulating layer in this order on the photoconductive layer.