JPH09146077A - Information recording medium and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the graininess of an information recording layer consisting of a liquid crystal phase and resin phase for recording optical information and to obtain an image free from the occurrence of image noise by constituting the resin phase of a UV-curing resin which is cured to a polymer at the time of curing of the information recording layer and an already polymerized resin which is already polymerized at the time of curing. SOLUTION: This information recording medium 3 has an electrode layer 13 used at the time of recording information on a substrate 15 and has the information recording layer 11 on this electrode layer 13. The information recording layer 11 consists of the liquid crystal phase and the resin phase. This resin phase consists of the already polymerized resin which is already polymerized at the time of curing in the forming process of the information recording layer 11 and the UV-curing resin which is cured to the polymer at the time of curing of the information recording layer 11. In the production of such information recording medium 3, a coating liquid contg. the liquid crystals, either of the UV-curing monomer or UV-curing oligomer, particulate resin, UV hardener and surfactant is applied on a base material and is then irradiated with UV rays, thereby, the coating liquid is cured.

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 as visible information by a method of exposing and recording while applying a voltage, and further to a method of manufacturing the information recording medium.

[0002]

2. Description of the Related Art An optical sensor having a photoconductive layer laminated on an electrode and an information recording medium having an information recording layer laminated on the electrode are arranged facing each other on the optical axis, and a voltage is applied between both electrode layers. An information recording / reproducing method in which information is recorded by aligning the liquid crystal layer by an electric field formed by an optical sensor while exposing, and reproducing the recorded information as transmitted information or reflected light as visible information is described above. 5-165005
No. 6-130347, Japanese Patent Application No. 5-26664.
Filed as No. 6. This information recording / reproducing method can visualize recorded information without using a polarizing plate. In such an information recording medium, the liquid crystal is extracted from the cross section of the information recording layer using hot methanol, dried, and then dried by a scanning electron microscope (Hitachi, S-800) at 10000.
When observing the internal structure at a magnification of 2, it was found that the surface of the layer was covered with a skin layer of an ultraviolet curable resin, and the inside of the layer had a structure in which a resin particle phase was filled in a liquid crystal phase forming a continuous layer. know. Although the cause of the resin particles has not been clarified, it is necessary for the memory property of the information recording medium to be exhibited.

However, on the other hand, the resin particles are one of the factors that give the graininess in the information recording layer, have a great influence on the finally obtained image, and cause the deterioration of the image quality as grain noise. In order to reduce the influence of the graininess and improve the image quality, the visual recognition degree of the graininess is reduced by making the resin particles smaller and reducing the graininess or making the particle size of the resin particles uniform. Although it is effective, the resin particles filled in the layer are generated by curing the ultraviolet curable resin component in the process of manufacturing the information recording layer, and the particles are always of a constant particle size and shape. However, it has been difficult to distribute it uniformly over the entire information recording layer.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to an improvement in an information recording medium using this type of liquid crystal-polymer composite, which has high sensitivity and good contrast,
It is an object to provide an information recording medium composed of an ultraviolet curable resin phase in which a resin phase of an information recording phase capable of recording information with good graininess is cured at the time of ultraviolet curing, and a high molecular weight resin which has already become high molecular weight at the time of curing. To do.

[0005]

The present invention has an information recording layer comprising a liquid crystal phase and a resin phase, the surface of which is covered with a skin layer of an ultraviolet curable resin, and a resin phase is formed in a continuous phase of liquid crystal. In the information recording medium described above, the resin phase is an information recording medium composed of an ultraviolet curable resin which is hardened to have a high molecular weight when the information recording layer is hardened and an already high molecular weight resin which has already been high molecular weight when hardened. In the above information recording medium, the already-high-molecular-weight resin is fine particles. The above information recording medium has a structure in which liquid crystals forming a continuous phase are filled with fine particles of an ultraviolet curable resin, a resin having a high molecular weight, or a continuous phase of fine particles. Particle size of fine particles is 1μ
The information recording medium is m or less. The information recording medium as described above, wherein the information recording layer contains a fluorinated surfactant. The information recording medium has an information recording layer having a memory property.

Further, in an information recording medium in which an electrode layer, a photoconductive layer, an information recording layer, and an electrode layer are sequentially provided, at least one electrode is transparent, and the surface of the information recording layer is a UV curable resin skin layer. In the information recording medium in which the resin phase is formed in the continuous phase of the liquid crystal, the resin phase is an ultraviolet curable resin that is cured during curing of the information recording layer and an already-polymerized resin that has already been polymerized during curing. It is an information recording medium consisting of. In an information recording medium in which an electrode layer, a photoconductive layer, a dielectric layer, an information recording layer, and an electrode layer are sequentially provided, at least one of the electrodes is transparent, and the information recording layer is a skin layer of an ultraviolet curable resin. In the information recording medium in which the resin phase is formed in the continuous phase of the liquid crystal which is coated, the mixed solution of the liquid crystal and the resin forming material is applied on the electrode and then cured by ultraviolet irradiation to form the surface. In an information recording medium formed on a skin layer made of only an ultraviolet curable resin, an information recording medium in which a resin phase comprises an ultraviolet curable resin cured at the time of curing the information recording layer and an already-polymerized resin which has already become high molecular weight at the time of curing. Is.

The above-mentioned information recording medium is one in which the high molecular weight resin is fine particles. The above information recording medium has a structure in which liquid crystals forming a continuous phase are filled with fine particles of an ultraviolet curable resin, a resin having a high molecular weight, or a continuous phase of fine particles. The above information recording medium has a particle diameter of 1 μm or less. The information recording medium as described above, wherein the information recording layer contains a fluorinated surfactant. The information recording medium has an information recording layer having a memory property.

Further, there is manufactured an information recording medium having an information recording layer composed of a liquid crystal phase and a resin phase, the surface of which is covered with a skin layer of an ultraviolet curable resin, and the resin phase being formed in the continuous phase of the liquid crystal. In the method, liquid crystal, at least one of an ultraviolet curable monomer or an ultraviolet curable oligomer, a fine particle resin, an ultraviolet curing agent, a coating solution containing a surfactant is applied to a substrate and then irradiated with ultraviolet rays to be cured. A method of manufacturing a recording medium.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a diagram for explaining a cross section of a first information recording medium of the present invention. The information recording medium 3 has an electrode layer 13 used for recording information on a substrate 15 and an information recording layer 11 on the electrode layer. Information recording layer 1
No. 1 is composed of a liquid crystal phase and a resin phase, and a smectic liquid crystal, a nematic liquid crystal, a cholesteric liquid crystal or a mixture thereof can be used as a liquid crystal material. It is preferable to use a smectic liquid crystal from the viewpoint of so-called memory property, which is retained for a long time. As a smectic liquid crystal,
Liquid crystal substances exhibiting a smectic A phase such as cyanobiphenyl type, cyanoterphenyl type, phenyl ester type having a long carbon terminal group of a substance exhibiting liquid crystallinity, and smectic used as a ferroelectric liquid crystal Examples thereof include a liquid crystal substance exhibiting a C phase, a liquid crystal substance exhibiting smectic H, G, E, F and the like. A nematic liquid crystal may be used, and the memory property can be improved by mixing with a smectic liquid crystal or a cholesteric liquid crystal, for example, a Schiff base type, an azoxy type, an azo type, a benzoic acid phenyl ester type, 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.

The resin phase is composed of an already-high molecular weight resin which has already been made high molecular weight during the curing in the process of forming the information recording layer and an ultraviolet curable resin which is hardened and becomes high molecular weight at the time of curing the information recording layer. The molecular weight resin is a resin to be mixed as a resin in the coating liquid when preparing the coating liquid for forming the information recording layer, and it is preferable that the resin has a fine particle shape from the beginning. The ultraviolet curable resin which is sometimes cured to have a high molecular weight is one in which at least one of an ultraviolet curable monomer and an ultraviolet curable oligomer is polymerized by irradiation of ultraviolet rays to form a resin phase.

Examples of the already high molecular weight resin include acrylic resin, methacrylic resin, polyester resin, polystyrene resin, silicone resin, and copolymers thereof, which are used for forming fine particles and forming an information recording layer. Those that are difficult to dissolve in a common solvent are preferable. Hereinafter, the fine particles of the already-polymerized resin are also referred to as high-molecular fine particles.

Further, as such polymer fine particles, composite fine particles modified with other materials can also be used. Particularly, it is preferable that the refractive index of the resin layer is approximately the same as the ordinary refractive index of the liquid crystal material optically, and acrylic resin or methacrylic resin is preferably used.

The fine particles of the fine polymer particles have a primary particle diameter of 1
The particle size is preferably not more than μm, more preferably not more than 0.5 μm, and the one having a small particle size is preferable from the viewpoint of improving the graininess. Further, if it is larger than 2 microns, obvious graininess appears, and the image is not improved. Further, the particle size is preferably uniform. Specifically, MP-1000 and M, which are fine particles made of polymethylmethacrylate resin and having a particle size of 0.4 to 0.8 μm,
P-1100, MP-1201, MP-1401, MP
-1450, MP-1451, MP-1220, MP-
2701 (manufactured by Soken Chemical Industry Co., Ltd.), particle size 0.4 composed of a copolymer of methyl methacrylate and divinylbenzene
MP-3000, MP-4000, which are fine particles of μm
MP-5000 (manufactured by Soken Kagaku) and the like can be mentioned.

As the compound forming the UV-curable resin phase, a compound which is compatible with the liquid crystal at room temperature or by heating in the state of monomer or oligomer, or at room temperature in a solvent common to the liquid crystal material in the state of monomer or oligomer. Examples thereof include those which are compatible with each other when or when heated. Specific examples thereof include acrylic acid esters and methacrylic acid esters, and in the state of monomers and oligomers, for example, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, isocyanuric acid. Polyfunctional monomers such as acid (ethylene oxide modified) triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, etc. or polyfunctional urethane-based, ester-based oligomers, and nonylphenol Modified acrylate, N-vinyl-2-pyrrolidone, 2-hydroxy-3-phenoxypropyl acrylate Mentioned monofunctional monomer or oligomer of.

The hard and high molecular weight resin forming the resin phase and at least one of the UV-curable monomer and the oligomer are used in a ratio of 1: 1 to 10: 1. If the ratio of the prepolymerized resin is too small, the effect of controlling the granularity by the prepolymerized resin cannot be obtained, and if the ratio of the prepolymerized resin is too large, the formation of the surface skin phase is hindered. The common solvent must be a common solvent for at least one of liquid crystal, an ultraviolet curable monomer or an oligomer, a photocuring agent, and a fluorosurfactant, and a poor solvent for polymer particles. Is. Specifically, methanol, ethanol, isopropanol, n-propanol, sec-butanol, isobutanol, n-butanol, methylisobutylcarbinol, diisobutylcarbinol, hexylene glycol, acetic acid-sec-butanol, cyclohexanone,
n-Hexane etc. can be mentioned.

Examples of the photo-curing agent include 2-hydroxy-2-methyl-1-phenylpropan-1-one (“Darocur 1173” manufactured by Ciba Geigy), 1-hydroxycyclohexyl phenyl ketone (“Irgacure manufactured by Ciba Geigy”). 184 "), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-
1-on (“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 (Nippon Kayaku Co., Ltd. “Kayacure DETX”) and ethyl p-dimethylaminobenzoate (Nippon Kayaku Co., Ltd. “Kayacure EPA”),
Isopropyl thioxanthone (a mixture of "Kuntacure ITX" manufactured by Ward Brekinsop and ethyl p-dimethylaminobenzoate, etc., and the like.
-Hydroxy-2-methyl-1-phenylpropane-1
-One is particularly preferred in terms of compatibility.

In addition to the wettability of the information recording layer with respect to the electrode layer, a fluorine-containing surfactant is added for the purpose of forming a skin layer made of only resin on the surface of the information recording layer. Examples of such a fluorine-based surfactant include Florade FC-430 and FC-431 (produced by Sumitomo 3M Limited), and N- (n- produced by Mitsubishi Materials Co., Ltd.
Propyl) -N- (β-acryloxyethyl) -perfluorooctyl sulfonic acid amide (EF-125M),
N- (n-propyl) -N- (βmethacryloxyethyl) -perfluorooctylsulfonic acid amide (EF-
135M), perfluorooctane sulfonic acid (EF-
101), perfluorocaprylic acid (EF-201),
N- (n-propyl) -N-perfluorooctanesulfonic acid amide ethanol (EF-121), and further EF-
102, EF-103, EF-104, EF-105,
EF-112, EF-121, EF-122A, EF-
122B, EF-122C, EF-122A3, EF-
123A, EF-123B, EF-132, EF-30
1, EF-303, EF-305, EF-306A, E
F, 501, EF-700, EF-201, EF-20
4, EF-351, EF-352, EF-801, EF
-802, EF-125DS, EF-1200, EF-
L102, EF-L155, EF-L174, EF-L
215 and the like. In addition, 3- (2-perfluorohexyl) ethoxy-1,2-dihydroxypropane (MF-100], Nn-propyl-N-2,3-dihydroxypropylperfluorooctylsulfonamide (MF-110), 3- (2-perfluorohexyl) ethoxy-1,2-epoxypropane (MF-12
0), N-n-propyl-N-2,3-epoxypropyl perfluorooctyl sulfonamide (MF-13
0), perfluorohexyl ethylene (MF-14
0), N- [3- (trimethoxysilyl) propyl] perfluoroheptylcarboxylic acid amide (MF-15
0), N- [3- (trimethoxysilyl) propyl] perfluoroheptylsulfonamide (MF-160) and the like. The fluorine-based surfactant is used in a proportion of 0.1 to 20% by weight based on the total amount of the liquid crystal and the resin forming material. Further, if necessary, a leveling agent may be added to improve the coating suitability of the solution and improve the surface property.

The content ratio of liquid crystal in the information recording layer is 1
It is 0% to 90% by weight, preferably 40% 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 aligned by information recording, and when it exceeds 90% by weight, the phenomenon such as seepage of the liquid crystal occurs.
Image unevenness is not preferable. Further, according to the present invention, the outer surface of the information recording layer can be a skin layer made of a resin layer. As a result, the ratio of liquid crystal is 40% by weight to
The liquid crystal content can be increased to 80% by weight, an information recording medium with high sensitivity and high contrast can be obtained, and the operating voltage can be lowered. In addition, the information recording layer is opaque due to light scattering when the electric field is not applied by making the ordinary refractive index of the liquid crystal phase and the refractive index of the resin phase substantially equal to the light used for information recording. When an electric field is applied, the liquid crystal phase is oriented, and the opacity of the information recording portion can be reduced. A polarizing plate is not required for reproducing information, and the optical system for reading can be simplified.

Next, as the method of forming the information recording layer, at least one of liquid crystal, polymer fine particles, ultraviolet curable monomer or oligomer, a photopolymerization initiator and a surfactant are mixed with a common solvent to form a solid content. A mixed solution having a concentration of 10 to 60% by weight is used. Solution viscosity is 1 to 500 cP
(20 ° C), preferably 10 to 200 cP (20 ° C). 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 above the temperature at which the liquid crystal maintains an isotropic phase, preferably within a range of an isotropic phase transition point or a temperature higher than the isotropic phase transition point by 10 ° C. to dissolve and disperse the mixed solution on the electrode layer. Under a room temperature condition, a coating method such as a spin coater, a bar coater, a blade coater, or a roll coater is applied to obtain a uniform film thickness. Next, the dried coating layer is irradiated with ultraviolet rays to be cured, but when the coating layers are irradiated with ultraviolet rays, infrared rays are shielded,
By irradiating with energy of 0.1 mJ / cm ² or more, an information recording layer excellent in phase separation between the liquid crystal phase and the resin phase can be obtained.

When the information recording layer is formed in this way,
0.1% to 20% of the thickness of the information recording layer on the surface of the information recording layer
And the inside of the information recording layer is filled with primary particles having the particle size of the polymer particles added as the already-polymerized resin, and / or the polymer particles. It is possible to have a structure in which primary particles having a particle diameter of 1 are connected and a liquid crystal phase is connected between them.

If the phase separation between the liquid crystal phase and the resin phase is incomplete in the fine structure inside the information recording layer,
The problem arises that the contrast cannot be obtained. In addition, when the phase separation is incomplete, the resistance of the information recording layer itself becomes low, and when information is recorded by the action of the electric field of electrostatic information using an optical sensor, a voltage is effectively applied to the liquid crystal phase in the information recording layer. Not applied, the liquid crystal drive becomes slow,
There is a problem of reduced sensitivity. Further, if the phase separation is incomplete, at least one of the UV-curable monomer and the oligomer is irradiated with an infrared ray-containing ultraviolet ray lamp to cause non-uniform shrinkage due to unnecessary heating. As a result, a serious problem occurs that a fatal uniform and homogeneous information recording layer cannot be formed.

The average film thickness of the information recording layer is 1 μm to 30 μm.
m is preferred. If the film thickness is too thick, the operating voltage will be high, but generally it is better to make the film thickness thinner for higher sensitivity and thicker for higher contrast. In order to provide excellent sensitivity and contrast ratio, the film thickness is preferably 3 μm to 20 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 0.1% to 20% of the thickness of the information recording layer,
If it is too thin, the liquid crystal will seep out, which will cause noise when information is recorded by an optical sensor described later. Although the detailed reason for the thickness of the skin layer is unknown, it 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 is required to be applied accurately and uniformly. However, by forming the information recording layer by the above method, the uniformity of the film thickness is 5 μm to 10 μm. The surface roughness can be within 20 nm,
It is possible to prevent uneven contrast and to prevent a shading phenomenon during information recording.

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. When the content of the liquid crystal is large, such as a layer, and the resin forms a phase in the form of particles, the liquid crystal is dispersed like a general polymer-dispersed liquid crystal in which the liquid crystal is dispersed in a generally known resin phase. Unlike the case where the content ratio is low, it is not necessary to consider the domain size of the liquid crystal so much, and it is possible to easily provide an information recording medium having high sensitivity and high contrast ratio. Further, on the surface of the information recording layer of the present invention,
The formation of the skin layer can prevent the liquid crystal from seeping out, but in order to further increase the surface hardness of the liquid crystal layer, a thermoplastic resin film, a thermosetting resin film, an ultraviolet curable resin, or the like is formed on the information recording layer. A layer may be formed by applying an ionizing radiation curable resin film or the like.

As a material for forming these resin layers, polyethylene terephthalate, polyethylene, polypropylene, ultraviolet ray and electron beam curable resins and the like are particularly preferable, 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
˜20 μm, 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 during information recording becomes low. It needs to be high. 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 intensity 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 has a specific resistance value of 10 ⁶ Ω · cm or less. A film, an inorganic metal oxide conductive film such as indium tin oxide (ITO), an organic conductive film such as a quaternary ammonium-containing substance, and the like. The electrode layer is formed by a method such as vapor deposition, sputtering, CVD, coating, plating, dipping and electrolytic polymerization. In addition, the film thickness depends on the electrical characteristics of the material forming the electrode,
It is necessary to change the voltage depending on the applied voltage at the time of information recording, but for example, an ITO film has a thickness of about 10 to 300 nm, and is formed on the entire surface between the information recording layer and 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-reflective, a metal electrode such as aluminum may be used. The light reflecting layer may be, for example, a dielectric mirror layer, and may be provided on at least one side or both sides of the electrode layer.

The substrate 15 may be either transparent or opaque depending on the reading of information by transmitted light or reflected light. The information recording medium may have a shape such as a card, a film, a tape, a disk, etc., but a support is required to strongly support the information recording medium, but when the information recording layer has supportability. There is no need to install it. The material and thickness of the support are not particularly limited, and for example, a flexible plastic film, glass, plastic sheet or card, etc. are used. Specifically, a flexible plastic film is used when the information recording medium takes the form of a flexible film, tape, disk, or card, and a rigid plastic sheet when strength is required. Inorganic materials such as glass are used.

When reproducing information with transmitted light,
If necessary, a layer having an antireflection effect may be laminated on the substrate, the transparent substrate may be adjusted to a film thickness capable of exhibiting the antireflection effect, or the both may be combined to provide the antireflection property.

Next, an information recording method on the first information recording medium of the present invention will be described. The information is recorded by using a method such as an optical sensor, heat, laser, corona charging or the like, but it is preferable to record the information by using an optical sensor.

The photosensor is formed by laminating an electrode layer and a photoconductive layer on a transparent substrate, and the photoconductive layer has a charge generation function and a charge transport function corresponding to information light at the same time. There are a layer type and a laminated type 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. In particular, an electric field exists. This is a layer in which the effect is remarkable.

The single-layer type photoconductive layer is formed of an inorganic photoconductive material or an organic photoconductive material. Se, Se—Te, ZnO, TiO ₂ , S
i, CdS, and the like, a vapor deposition method, a sputtering method,
A single or a mixture of 5 to 3 is formed on the electrode layer by the CVD method or the like.
The film is laminated with a film thickness of 0 μm, preferably 20 to 30 μm. In addition, the above-mentioned inorganic photoconductor as fine particles, organic insulating resin, for example, silicone resin, polyester resin,
It may be dispersed in a polycarbonate resin, a styrene-butadiene resin, a styrene resin, a polyvinyl acetal resin or the like to form a photoconductive layer. In this case, 0.1 to 10 parts by weight of photoconductive particles, preferably 1 part by weight of the resin, is preferable. 1 to
It is preferable that the particles are dispersed at a ratio of 5 parts by weight.

The organic photoconductive substance includes a polymer photoconductive substance and a dispersion of a low molecular weight photoconductive substance in an insulating binder. Examples of the polymer photoconductive substance include polyvinylcarbazole (hereinafter, also referred to as PVK),
Poly-containing an ethylenically unsaturated group such as an allyl group or an acryloxyalkyl group instead of the vinyl group in PVK
N-ethylenically unsaturated group-substituted carbazoles and poly-N-ethylenically unsaturated group-substituted phenothiazines such as poly-N-acrylphenothiazine and poly-N- (β-acryloxy) phenothiazine 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 after drying of these organic photoconductive substances is 5 to 30 μm, preferably 10 to 30 μm, and laminated on the electrode. Next, the stacked photoconductive layer is formed by sequentially stacking a charge generation layer and a charge transport layer on the electrode. The photoconductive layer includes an inorganic material photoconductive layer and an organic material photoconductive layer.

The charge generation layer in the inorganic material photoconductive layer is
Se-Te, Si doped with sulfur, oxygen, or the like is deposited on the electrode by a vapor deposition method, a sputtering method, a CVD method, or the like.
The film is laminated to a film thickness of 0.05 μm to 1 μm. Then, Se, As ₂ S as a charge transport layer is formed on this charge generation layer.
e _3, Si, may be formed by laminating a film thickness of 10μm~50μm analogously doped with Si or the like, such as methane.

Next, the charge generating layer in the organic material photoconductive layer comprises a charge generating substance and a binder, and as the charge generating substance, there are fluorenone azo pigments, monoazo pigments, bisazo pigments, pyrrole pigments and azurenium. Salt pigments, phthalocyanine pigments, polycyclic aromatic pigments, pyrylium salt pigments, triazo pigments, squarylium salt pigments, perylene pigments, pyranthrone pigments, cyanine pigments, polycyclic quinone pigments, imidazole pigments and the like. Specific examples thereof include the charge-generating substances described in JP-A-6-265931.

Examples of the binder include silicone resin, styrene-butadiene copolymer resin, epoxy resin, acrylic resin, saturated or unsaturated polyester resin, polymethylmethacrylic acid resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-acetic acid. Examples thereof include vinyl copolymer resins, which are formed by dispersing the above charge generating substance in a binder. The charge-generating substance is preferably a fluorenone azo pigment or a bisazo pigment, and the binder is preferably a polyester resin or a vinyl chloride-vinyl acetate copolymer resin. The mixing ratio of the charge generating substance and the binder is 0.1 to 10 parts by weight, preferably 0.1 to 1 part by weight of the charge generating substance.
It is desirable to use at a ratio of 1 part by weight. The thickness of the charge generation layer after drying is 0.01 μm to 1 μm, preferably 0.1 μm to 0.3 μm.

The charge transport layer comprises a charge transport material and a binder. The charge-transporting substance is a substance having a good property of transporting charges generated by the charge-generating substance, and examples thereof include hydrazone-based, pyrarizone-based, polyvinylcarbazole-based, carbazole-based, oxazole-based, triazole-based, aromatic amine-based, amine-based, There are triphenylmethane-based, butadiene-based, stilbene-based, polycyclic aromatic compound-based, etc., and it is necessary to use a substance having a good hole transport property. Preferred are butadiene-based and stilbene-based charge-transporting substances, and specific examples thereof include the charge-generating substances described in JP-A-6-265931.

As the binder, the same binders as those mentioned above in the charge generating layer can be used, but polyvinyl acetal resin, styrene resin and styrene-butadiene copolymer resin are preferable. The binder is used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 1 part by weight, based on 1 part by weight of the charge transport material. The thickness of the charge transport layer after drying is 1 μm to 50 μm.
m, preferably 10 μm to 30 μm. As a combination of the charge generating substance and the charge transporting substance, a combination of the charge transporting substance of the bisazo pigment and the butadiene or hydrazone type charge transporting substance is preferable.

When the single-layer photoconductive layer or the laminated photoconductive layer is an organic photoconductive layer, dichloroethane as a solvent,
1,1,2-trichloroethane, monochlorobenzene,
Tetrahydrofuran, cyclohexane, dioxane,
1,2,3-trichloropropane, ethyl cellosolve,
1,1,1-trichloroethane, methyl ethyl ketone,
It is advisable to use chloroform, toluene or the like as a coating solution, and examples of the coating method include a blade coating method, a dipping method and a spinner coating method.

The photoconductive layer may be provided on the electrode via the charge injection control layer. The charge injection control layer is provided as necessary, 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. 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 contrast potential, which is the difference between the potential applied to the information recording layer in the exposed portion, that is, the bright potential, and the potential applied to the information recording layer in the unexposed portion, that is, the dark potential, is set large in the operation region of the liquid crystal. Is necessary.

Therefore, for example, the dark potential applied to the liquid crystal phase in the unexposed portion of the photoconductive layer needs to be set to about the operation start potential of the liquid crystal, and an electric field of 10 ⁵ to 10 ⁶ V / cm is applied to the photoconductive layer. Is required to have such a conductivity that a dark current of 10 ⁻⁴ to 10 ⁻⁸ / cm ² is generated, preferably 1 × 1.
The range of 0 ^{−6 to} 5 × 10 ⁻⁷ 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 oriented, and there is no difference in transmittance even when exposed. The optical sensor for recording optical information on the information recording medium of the present invention is such that the electric field or the amount of charge applied to the information recording medium at the time of light irradiation is amplified with the light irradiation, and the voltage is applied even after the light irradiation is finished. If it is continued, the conductivity is maintained, and the electric field or the amount of charge is continuously applied 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, 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
Denotes a shutter having a driving mechanism, 23 denotes a pulse generator (power supply), and 24 denotes a dark box. Electrodes 13, 13 '
When information light is incident from the light source 21 while voltage is applied by the pulse generator 23, photo carriers generated in the photoconductive layer 14 in the portion where the light is incident are generated by the electric field formed by both electrodes on the information recording layer 11 side. Then, the voltage is redistributed, the liquid crystal phase in the information recording layer 11 is aligned, and recording is performed according to the pattern of the information light. Although the photoconductor side is the positive electrode and the liquid crystal recording medium side is the negative electrode in the figure, the polarity is set according to the characteristics of the optical sensor. The applied voltage is set by appropriately setting the voltage distribution of the optical sensor, the air gap, and the information recording medium according to the operating voltage of the liquid crystal material, and setting the voltage applied to the information recording layer in the operating voltage region. Good to do. Information recording by this optical sensor is possible as planar analog recording, and since the orientation of the liquid crystal phase can be oriented at the electrostatic charge level, the same high resolution as silver salt photography can be obtained, and exposure is also possible. The pattern is retained by being visualized by the alignment of the liquid crystal phase.

As a method of inputting information to the first information recording medium 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 the photographic film used in a normal camera, and an optical shutter can be used as a recording member, and an electric shutter can also be used. I will get it. Also, 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. One for each of three R, G, and B information recording media.
Frames are formed, or R on the same information recording medium,
Color images can also be taken by recording G and B images side by side and recording them as one frame.

The laser recording method is as follows:
The light source is an argon laser (514.488n)
m), a helium-neon laser (633 nm), a semiconductor laser (780 nm, 810 nm, etc.) can be used,
This is performed by laser exposure scanning corresponding to an image signal, a character signal, a code signal, and a line drawing signal. 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, dot generator ON / OFF control is performed on laser light.

In the electrostatic information recorded on the information recording medium, when the information is reproduced by the transmitted light as shown in FIG. 3, the light A is transmitted because the liquid crystal is oriented in the electric field direction in the information recording portion. Then, the light B is scattered at a portion where no information is recorded, and contrast with the information recording portion is generated. The information recorded by the orientation of the liquid crystal is visible information that can be visually read, but it can also be read by enlarging it with a projector, and can be read with high accuracy by laser scanning or using a CCD. Can be read, and scattered light can be prevented by using a Schlieren optical system if necessary. Further, by making the electrode layer light-reflecting or laminating a light-reflecting layer on the electrode layer, it can be read by reflected light. It can also be reproduced by the information output device shown in FIG. In the figure, 41 is an information recording medium scanner, 42 is a personal computer, and 43 is a printer.

Next, the second information recording medium of the present invention will be described. The second information recording medium is one in which a photoconductive layer is incorporated into the first information recording medium, and it is not necessary to separately prepare an optical sensor for recording information, and information recording can be performed by itself.

FIG. 4 is a sectional view for explaining an information recording medium of the present invention integrated with an optical sensor. FIG. 4A shows an information recording medium in which a photoconductive layer and an information recording layer are directly laminated, 3 in the figure is an information recording medium, 11 is an information recording layer, 13,
13 'is an electrode layer, 14 is a photoconductive layer, and 15 is a substrate.
The photoconductive layer 14 laminated on the electrode 13 ′ is similar to 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 formed on the photoconductive layer. Are laminated in the same manner as the first information recording medium.

Further, according to the method for forming the first information recording layer, it is possible to prevent the liquid crystal from seeping out from the surface of the information recording layer.
Since the electrode layer 13 can be formed by vapor deposition by sputtering, the electrode layer 13 can have a high insulating property, and a noise-free information recording layer can be formed when information is recorded. The electrode layers 13 and 13 'can adopt the same material and forming method as the electrode layer in the first information recording medium described above, but transparency is required when reading information recording by transmitted light, When reading with reflected light, either one of the electrode layers may be made light reflective, or a light reflecting layer such as a dielectric mirror layer may be laminated on any one of the electrode layers. Further, a substrate may be laminated on the electrode 13 on the information recording layer.

FIG. 4B is a diagram for explaining an information recording medium in which the intermediate layer 12 is provided between the photoconductive layer 14 and the information recording layer 11. 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 due to the interaction depending on the solvent, or the photoconductive layer may be used as the 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, so that image unevenness occurs. Therefore, it is provided to prevent these problems. Examples of such an intermediate layer include inorganic materials such as SiO ₂ , TiO ₂ , CeO ₂ , Al ₂ O ₃ and Ge.
It is preferable to use O ₂ , Si ₃ N ₄ , AlN, TiN, MgF ₂ , ZnS, etc. and stack them by a vapor deposition method, a sputtering method, a CVD method or the like.

As the intermediate layer, an aqueous solution such as polyvinyl alcohol, water-soluble polyurethane, or water glass, which is a water-soluble resin having a low compatibility with the organic solvent used for forming the photoconductive layer or the information recording layer, is used. The layers may be laminated by a spin coating method, a blade coating method, a roll coating method or the like. Further, a coatable fluororesin may be used, and in this case, it 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. As the applicable fluororesin, the fluororesin described in JP-A-6-265931 can be used.

Further, in the case of an organic material which is formed into a film under vacuum, there is no fear of dissolving the photoconductive layer during the film formation. Among these materials, polyethylene, polypropylene, poly (monochlorotrifluoroethylene), polytetrafluoroethylene, etc. can be used as a material to be formed by a vapor deposition method.
Moreover, polyparaxylylene or the like can be used as a material for forming a film by the CVD method. Among these, it is particularly preferable to use polyvinyl alcohol, and when a saponification degree of 97% or more and a polymerization degree of 1500 or more is used, the formation of the information recording layer can be made excellent.

The intermediate layer must be incompatible with both the organic photoconductive layer-forming material and the information recording layer-forming material, and if it has conductivity, the diffusion of space charge will not occur. 10 ⁷ Ω due to deterioration of resolution.
Insulation of cm or more is required. Further, 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 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 applied, the type of solvent, and the viscosity, the thickness of the material to be laminated and coated may be appropriately set.
The intermediate layer is required to be transparent, and considering the voltage distribution applied to each layer, it is preferable to use a material having a high dielectric constant as well as a thin film. 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.

A method of recording information on the second information recording medium will be described with reference to FIG. First, electrode 1
When the information light 18 is incident while applying a voltage between 3 and 13 ′, the photocarriers generated in the photoconductive layer 14 in the portion where the light is incident move due to the electric field formed by both electrodes,
When the voltage is redistributed, the liquid crystal phase in the information recording layer is aligned, 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 applied voltage time, the voltage distribution in the information recording medium is set appropriately and the voltage distribution in the information recording layer is set in the operating voltage region of the liquid crystal. Good to do. This information recording method enables planar analog recording, and high resolution can be obtained 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. . Further, as the information input method, the same method as the method using a camera and the method using a laser described in the section of the first liquid crystal recording medium can be used. Further, a recording method using a laser can be similarly performed. Further, the spectral characteristics of the photoconductive layer do not need to be panchromatic, as long as they have sensitivity to the wavelength of the laser light source.

The information recorded on the second liquid crystal recording medium is
When reading with transmitted light, reproduction is performed with transmitted light from the information recording layer side similarly to the case of the first liquid crystal recording medium shown in FIG. 3, and also when reading with reflected light. Next, the second liquid crystal recording medium of the present invention is shown in FIG.
As shown in (c), an insulating light-reflecting layer 12 ′ and a transparent insulating layer 12 ″ may be provided between the photoconductive layer and the information recording layer in the second liquid crystal recording medium. Information can be read by making incident the reading light from the information recording layer side and reflecting the light.
Examples of 2'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 deposited from different vapor deposition sources at a deposition rate of aluminum oxide of 5 nm / sec and a deposition rate of germanium of 2 nm / sec. For example, a film having a film thickness of about 1 μm can be given by simultaneous vapor deposition.

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 reflection layer 12' is peeled off, and it is provided to prevent the peeling and improve the formation of the information recording layer 11. The transparent insulating layer 12 ″ is the same as the intermediate layer 12. The insulating light reflecting layer 12 ′ and the transparent insulating layer 12 ″ are similar to the intermediate layer in that the distribution voltage applied to the liquid crystal phase is applied. It is preferable that the film thickness is thin, because it may decrease or deteriorate the resolution, and the total film thickness may be 2 μm or less, preferably 0.1 to 1 μm. In this information recording medium, the read light does not pass through the generally colored photoconductive layer when reading the information, so that the reproduced information can be noise-free.

In the first and second liquid crystal recording media of the present invention, a primer for improving adhesion is provided between the respective layers such as the electrode layer, the light reflection layer or the light reflection prevention layer and the substrate. Layers 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 coated with an ionizing radiation curable resin such as a thermoplastic resin, a thermosetting resin, or an ultraviolet curable resin. Or in the case of a combination of an inorganic material and an organic material, a known silane coupling agent, an organic metal compound such as an organic titanium compound or an organic aluminum 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. It is a range. Since the voltage applied to the information recording layer can be controlled by improving the adhesion and changing the film thickness, it is possible to control the recordable exposure range.

Further, the first and second liquid crystal 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 cut surface is the information recording layer. The inside is exposed and the liquid crystal layer exudes during storage. When this bleeding phenomenon occurs, a problem arises in that when information is recorded, accurate information recording cannot be performed at the edge of the liquid crystal recording medium. In order to prevent this, after cutting the liquid crystal recording medium into an appropriate shape, a resin layer may be applied or laminated on the cut surface in the same manner as above to form the same, and the cut surface may be protected.

Further, the first and second liquid crystal recording media of the present invention record electrostatic information in a state in which the electrostatic information is visualized by the alignment of the liquid crystal. However, the visualized information is not erased and a memory property is added. The memory may be erased by heating to a high temperature near the isotropic phase transition, and can be used again for information recording.

The information recording medium in the present invention is an information recording medium having an information recording layer composed of a liquid crystal phase and a resin phase on an electrode layer, and the information recording layer uses a mixed solution of liquid crystal and a resin forming material as an electrode. In an information recording medium, which is formed by being cured by being irradiated with ultraviolet rays after being applied on the outer surface of the information recording medium and having a skin layer formed of only the ultraviolet curing resin, the resin layer constituting the information recording layer is the ultraviolet curing resin. It is composed of a component and a resin component having a high molecular weight. Especially since the existing high molecular weight resin component consists of polymer fine particles,
It is possible to easily obtain an information recording medium that has high sensitivity, good contrast, and enables recording of information with good graininess.

[0062]

EXAMPLES Examples will be described below, but "parts" in the examples
Indicates parts by weight and "%" indicates% by weight. Example 1 (Production of information recording medium) Thickly washed thickness of 1.1 mm
An indium tin oxide (ITO) film having a thickness of 100 nm was formed on the glass substrate of No. 1 by sputtering to obtain an electrode layer. On the obtained electrode, 4.5 parts of dipentaerythritol hexaacrylate, a photocuring initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one, manufactured by Ciba-Geigy, trade name Darocure 1173) 0.45.
Part, smectic liquid crystal (Merck, S-6) 10 parts,
1 part nematic liquid crystal (manufactured by Merck, BL-066), surfactant (manufactured by Sumitomo 3M, trade name Florard FC
-430) 0.2 parts of cyclohexane (manufactured by Junsei Kagaku Co., Ltd., special grade reagent) was uniformly dissolved, and further dissolved therein, fine polymer particles (manufactured by Soken Kagaku, MP-1451, particle size 0.15 μm) Was added to sufficiently disperse the polymer fine particles to prepare a coating liquid. This coating solution was applied using a spin coater, immediately held at 50 ° C. for 3 minutes, then held under reduced pressure for 2 minutes, and returned to atmospheric pressure, immediately after 500 m.
Ultraviolet light of J / cm ² was irradiated to form an information recording layer having a film thickness of 6 μm. The cut surface of the obtained information recording layer was extracted with hot methanol to dry the liquid crystal, and dried, and then 100 with a scanning electron microscope (Hitachi, S-800).
When the internal structure was observed at a magnification of 00, the surface of the layer was covered with an ultraviolet curable resin having a thickness of 0.6 μm, which corresponds to 10% of the film thickness, and the inside of the layer had a particle size of 0. 1
It was filled with resin particles of 5 μm and had a structure in which the added resin particles were continuous.

(Production of optical sensor) Area resistance 80 Ω / □ and film thickness 10 formed on a glass substrate having a thickness of 1.1 mm.
The 0 nm ITO film was thoroughly washed, and a disazo-based pigment dispersion liquid (DPDD-3,
Daiichi Seika Kogyo Co., Ltd., pigment: binder resin = 3: 2 ratio, solid content 2%) was used as a coating liquid, and was coated with a blade coater, air-dried, and then dried at 100 ° C. for 1 hour to obtain a film thickness of 0.3 μm.
m of charge generation layers were laminated. Then, the following structure was formed on the charge generation layer as a charge transporting substance.

[0064]

Embedded image

5 parts by weight of the butadiene derivative and a polycarbonate resin (manufactured by Mitsubishi Gas Chemical Co., Inc., Iupilon Z2)
00) 1 part by weight and 24 parts by weight of toluene are uniformly dissolved to obtain a coating solution, which is applied with a spinner at 500 rpm for 0.4 seconds to form a film on the surface of the coating film, and the surface of the coating film is attached. Until it disappears, it is left in the windless state, leveled and dried, and then dried at 80 ° C. for 2 hours to laminate a charge transport layer, and a film thickness of 10 μm including a charge generation layer and a charge transport layer.
An optical sensor according to the present invention having m photoconductive layers was prepared. When the electrical characteristics of this optical sensor were measured, it showed a photo-induced current amplification effect.

(Information recording method and recording characteristics) Next, the optical sensor and the information recording medium 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. A DC voltage of 700 V was applied for 0.04 seconds with the recording medium side as a negative, and at the same time, exposure was performed from the photosensor side using a halogen lamp having an illuminance of 100 lux as a light source for 1/30 seconds to photograph a gray scale. After the exposure was completed, the information recording medium was taken out and the information recording medium was observed with transmitted light. As a result, a recording portion corresponding to a gray scale was observed in the information recording layer. Then, using the xenon lamp as a light source, the information recording medium was used as the information output device shown in FIG. 11 by the image scanner using the CCD line sensor, and the wavelength light was passed through the wavelength filter (357 nm, half-value width 10 nm). Read the recorded information with a sublimation transfer printer (SP-5500 manufactured by Victor Company of Japan)
As a result of outputting information at a final magnification of 10 times using, a good printed matter having gradation characteristics corresponding to gray scale was obtained, and almost no granular noise was observed in this printed matter. Also, when a color image was recorded in the same manner by separating it into three colors of R, G, and B by a prism and a color filter, the recorded image was good, and the recorded information of the color image was read in the same way and the information was output. Good prints were obtained, and almost no granular noise was observed on the prints.

Comparative Example 1 (Preparation of Information Recording Medium) A 100 nm-thick indium tin oxide (ITO) film was formed by sputtering on a sufficiently washed glass substrate having a thickness of 1.1 mm to obtain an electrode layer. . On the obtained electrode, 9 parts of dipentaerythritol hexaacrylate, a photocuring initiator (2-hydroxy-
2-Methyl-1-phenylpropan-1-one, 0.45 parts by trade name Darocur 1173 manufactured by Ciba-Geigy, 10 parts smectic liquid crystal (S-6 manufactured by Merck), nematic liquid crystal (BL-066 manufactured by Merck) ) 1 part, surfactant (trade name: Florard FC-4 manufactured by Sumitomo 3M Limited)
30) 0.2 parts was evenly dissolved in 22 parts of cyclohexane (Junsei Kagaku Reagent Special Grade) to prepare a coating solution. This coating solution was applied using a spin coater, immediately held at 50 ° C. for 3 minutes, then held under reduced pressure for 2 minutes, returned to atmospheric pressure, and immediately irradiated with UV light of 500 mJ / cm ^2. An information recording layer having a film thickness of 6 μm was formed. After the liquid crystal was extracted from the cut surface of the obtained information recording layer using hot methanol and dried, the internal structure was observed with a scanning electron microscope (S-800 manufactured by Hitachi, Ltd.) at a magnification of 10000. The surface of 0. corresponds to 10% of the film thickness.
The layer was covered with an ultraviolet curable resin having a thickness of 6 μm, and the inside of the layer was filled with resin particles having an average particle diameter of 0.15 μm, but the particle diameter varied from 0.05 to 0.3 μm.

(Information Recording Method and Recording Characteristics) Next, a gray scale was photographed in the same manner as in Example 1. After shooting, the information recording medium was read in the same manner as in Example 1, and the recorded information was recorded by a sublimation transfer printer (manufactured by Victor Company of Japan, Ltd.).
As a result of outputting information at a final magnification of 10 times using SP-5500), although a printed matter having gradation corresponding to gray scale was obtained, granular noise was clearly seen in this printed matter, which was excellent. It was not a printed matter.
In addition, R, G, B are provided by the prism and color filter.
When the color image was recorded in the same manner by separating the three colors
The recorded image was good, and as a result of similarly reading the recorded information of the color image and outputting the information, a color image printed matter was obtained, but in this printed matter granular noise was clearly seen and it could not be said to be a good printed matter. It was

Example 2 (Preparation of Information Recording Medium) A 100 nm thick indium tin oxide (I
A (TO) film was formed by sputtering to obtain an electrode layer. On the obtained electrode, 0.8 part of dipentaerythritol hexaacrylate, a photo-curing initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one, Ciba-Geigy product name Darocur 1173) 0.4
5 parts, smectic liquid crystal (M-6, S-6) 10
Part, nematic liquid crystal (manufactured by Merck, BL-066) 1
Solution, 0.2 parts of a surfactant (Sumitomo 3M, trade name: Florard FC-430), was uniformly dissolved in 22 parts of cyclohexane (Junsei Kagaku, special grade reagent),
Further, polymer fine particles (MP-14, manufactured by Soken Chemical Industry Co., Ltd.)
51 parts, particle size 0.15 micron) was added and the fine particles were sufficiently dispersed to prepare a coating solution. This coating solution was applied using a spin coater, immediately held at 50 ° C. for 3 minutes, then held under reduced pressure for 2 minutes, returned to atmospheric pressure, and immediately irradiated with UV light of 500 mJ / cm ^2. Film thickness 6
A μm information recording layer was formed. A liquid crystal was extracted from the cut surface of the obtained information recording layer using hot methanol and dried, and then a scanning electron microscope (S-80, manufactured by Hitachi, Ltd.).
0), the internal structure was observed at 10000 times. The surface of the layer was covered with a UV-curing resin having a thickness of 0.2 μm, which corresponds to 3.3% of the film thickness, and the inside of the layer had an average particle size of 0.1.
It was filled with resin particles of 5 μm and had a structure in which the added resin particles were continuous. The particle size was almost uniform.

(Information Recording Method and Recording Characteristics) Next, a gray scale was photographed in the same manner as in Example 1. After shooting, the information recording medium was read in the same manner as in Example 1, and the information was read by a sublimation transfer printer (SP manufactured by Victor Company of Japan).
As a result of outputting the information at a final magnification of 10 times using -5500), a printed matter having gradation corresponding to the gray scale was obtained, but in this printed matter, granular noise was clearly seen and a good printed matter was obtained. I couldn't say that. When a color image was recorded in the same manner by separating into three colors of R, G, and B by a prism and a color filter, the recorded image was good, and the recorded information of the color image was read in the same way and the information was output. In this printed matter, almost no granular noise was observed, and the color printed matter was good.

Example 3 On the photoconductive layer of the optical sensor prepared in Example 1, a fluororesin (manufactured by Asahi Glass Co., Ltd., Cytop, water absorption 0.01%, specific resistance 1 × 10 ¹⁸ Ω · cm) was perfluoro. Dissolve in 2-butyltetrahydrofuran and apply a 4.5% solution of the solution with a spinner at 1500 rpm for 20 seconds.
After drying at 0 ° C. for 1 hour, an intermediate layer made of a transparent insulating layer having a film thickness of 1 μm was formed. Next, on the intermediate layer, 4.5 parts of dipentaerythritol hexaacrylate, a photocuring initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one, manufactured by Ciba-Geigy, trade name Darocure 1173). 45 parts, smectic liquid crystal (Merck, S-6) 10 parts, nematic liquid crystal (Merck,
BL-066) 1 part and a surfactant (Sumitomo 3M Co., Ltd. trade name Florard FC-430) 0.2 part, were uniformly dissolved in 22 parts of cyclohexane (Junsei Kagaku, special grade reagent), and further, Polymer fine particles (manufactured by Soken Chemical Industry, MP
-1451, particle size 0.15 micron) 4.5 parts,
The fine particles were sufficiently dispersed to prepare a coating solution. Apply this coating solution using a spin coater and immediately apply 50
After the temperature was maintained at 3 ° C. for 3 minutes, the pressure was maintained for 2 minutes under reduced pressure, the pressure was returned to the atmospheric pressure, and then an ultraviolet ray of 500 mJ / cm ^{2 was} immediately irradiated to form an information recording layer having a thickness of 6 μm. Further, a 50 nm-thick gold film was formed as an upper electrode on this information recording layer by a vapor deposition method to prepare a second information recording medium of the present invention. After the liquid crystal was extracted from the cut surface of the obtained information recording layer using hot methanol and dried, the internal structure was observed with a scanning electron microscope (S-800 manufactured by Hitachi, Ltd.) at a magnification of 10000. Is covered with an ultraviolet curable resin having a thickness of 0.6 μm corresponding to 10% of the film thickness, and resin particles having an average particle diameter of 0.15 μm are filled inside the layer.
Further, it had a structure in which the added resin particles were continuous. The particle size was almost uniform.

(Information Recording Method and Recording Characteristics) Next, this information recording medium is made as shown in FIG.
With the information recording medium side as negative, a DC voltage of 700 V is set to 0.
Simultaneously with application for 04 seconds, the illuminance from the optical sensor side is 10
1 / exposure using a halogen lamp of 00 lux as the light source
It was performed for 30 seconds, and a gray scale was photographed. After the exposure was completed, the information recording medium was taken out, and the information recording medium was observed with transmitted light. As a result, a recording portion composed of a light transmitting portion corresponding to a gray scale was observed in the information recording layer. Then
As a result of outputting the recorded information on the information recording medium in the same manner as in Example 1, a good printed matter having gradation corresponding to gray scale was obtained, and granular noise was hardly seen in this printed matter. Further, as in the case of Example 1, the recorded information of the color image was similarly read and the information was output. As a result, a good printed matter was obtained, and granular noise was hardly seen in this printed matter.

[0073]

INDUSTRIAL APPLICABILITY At the time of producing an information recording medium in which the surface of the information recording layer composed of the liquid crystal phase and the resin phase is formed into the skin layer composed of only the ultraviolet curable resin, at least one of liquid crystal, ultraviolet curable monomer or oligomer is used. Since the polymer fine particles are added to the coating liquid containing either one, the granular characteristics of the resin phase are improved, and an information recording medium that enables high-sensitivity, good contrast and good granularity information recording is obtained. be able to.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an information recording medium of the present invention.

FIG. 2 is a diagram illustrating an information recording device incorporating an optical sensor.

FIG. 3 is a diagram illustrating a method of reproducing information recorded on an information recording medium.

FIG. 4 is a sectional view illustrating an information recording medium of the present invention integrated with an optical sensor.

FIG. 5 is a cross-sectional view illustrating a method of recording information on an information recording medium integrated with an optical sensor.

FIG. 6 is a diagram illustrating an output device of information recorded on an information recording medium.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Optical sensor, 3 ... Information recording medium, 11 ... Information recording layer, 12 ... Intermediate layer, 13, 13 '... Electrode layer, 14 ... Photoconductive layer, 15 ... Substrate, 18 ... Information light, 19 ... Spacer,
21 ... Light source, 22 ... Shutter having drive mechanism, 23
… Pulse generator (power supply), 24… Dark box, 41…
Information recording medium scanner, 42 ... PC, 43 ... Printer

Claims (14)

[Claims] 1. An information recording medium having an information recording layer comprising a liquid crystal phase and a resin phase, the surface of which is covered with a skin layer of an ultraviolet curable resin, and the resin phase being formed in a continuous phase of liquid crystal, An information recording medium, characterized in that the resin phase is composed of an ultraviolet curable resin which is hardened and has a high molecular weight when the information recording layer is hardened, and an already high molecular weight resin which has a high molecular weight when hardened. 2. The information recording medium according to claim 1, wherein the high molecular weight resin is fine particles. 3. A liquid crystal having a continuous phase, wherein the liquid crystal has a structure in which ultraviolet curable resin, fine particles made of a prepolymerized resin, or a continuous phase of fine particles is filled. Information recording medium. 4. The information recording medium according to claim 2, wherein the fine particles have a particle diameter of 1 μm or less. 5. The information recording medium according to claim 1, wherein the information recording layer contains a fluorinated surfactant. 6. The information recording medium according to claim 1, wherein the information recording layer has a memory property. 7. An information recording medium in which an electrode layer, a photoconductive layer, an information recording layer, and an electrode layer are sequentially provided, and at least one of the electrodes is transparent, and the information recording layer has a skin whose surface is an ultraviolet curable resin. In an information recording medium in which a resin phase is formed in a continuous phase of liquid crystal, which is covered with a layer, the resin phase is an ultraviolet curable resin that is cured when the information recording layer is cured and an already-polymerized resin that is already high molecular weight when cured An information recording medium comprising: 8. An information recording medium having an electrode layer, a photoconductive layer, a dielectric layer, an information recording layer, and an electrode layer, which are sequentially provided, and at least one of the electrodes is transparent, and the surface of the information recording layer is ultraviolet-cured. In an information recording medium that is covered with a resin skin layer and has a resin phase formed in the continuous phase of liquid crystal, the resin phase is a UV curable resin that is cured when the information recording layer is cured, and a high molecular weight resin that is already high when cured. An information recording medium comprising a molecular weight resin. 9. The information recording medium according to claim 7, wherein the high molecular weight resin is fine particles. 10. A structure in which a liquid crystal forming a continuous phase is filled with ultraviolet curable resin, fine particles of an already high molecular weight resin, or a continuous phase of fine particles. 8. The information recording medium described in 8. 11. The information recording medium according to claim 9, wherein the fine particles have a particle diameter of 1 μm or less. 12. The information recording medium according to claim 7, wherein the information recording layer contains a fluorinated surfactant. 13. The information recording medium according to claim 7, wherein the information recording layer has a memory property. 14. An information recording medium having an information recording layer comprising a liquid crystal phase and a resin phase, the surface of which is covered with a skin layer of an ultraviolet curable resin, and the resin phase being formed in a continuous phase of liquid crystal. In the method, a coating liquid containing at least one of liquid crystal, an ultraviolet curable monomer or an ultraviolet curable oligomer, a fine particle resin, an ultraviolet curing agent, and a surfactant is applied to a substrate and then irradiated with ultraviolet rays to be cured. A method for manufacturing an information recording medium characterized by the above.