JPH08167182A - Information recording medium integrated with package - Google Patents

Abstract

PURPOSE: To perform high resolution recording by combining an optical sensor with an information recording medium with a liq. crystal recording layer as a structural element. CONSTITUTION: A liq. crystal recording medium obtd. by laminating a liq. crystal recording layer 22 contg. a liq. crystal dispersed and fixed in a resin on a 1st electrode layer 3 is combined with an optical sensor 29 obtd. by forming a 2nd electrode layer 6 and a photoconductive layer 21 on a transparent substrate 1 so that the recording layer 22 confronts the photoconductive layer 21 optionally with a middle layer 31 in-between. The resultant information recording medium 30 is made square, such media are radially arranged on a disk substrate 1 with a central hole and this substrate 1 is rotatably housed in a housing case with a window which is opened and shut by a shutter. The objective information recording medium capable of being incorporated into a camera, etc., is obtd. and high resolution recording is performed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an integrated information recording medium in which an optical sensor and a liquid crystal recording medium are laminated and an image is recorded by changing the orientation of the liquid crystal recording medium, and in particular, an integrated information recording medium on a disc substrate. The present invention relates to a packaging-integrated information recording medium in which a plurality of media are radially formed and packaged.

[0002]

2. Description of the Related Art An optical sensor consisting of a photoconductive layer having an electrode provided on the front surface and an information recording medium consisting of a charge holding layer having an electrode provided on the rear surface of the photosensor are arranged on the optical axis. Then, exposure is performed while applying voltage between both conductive layers, electrostatic charge is recorded on the charge holding layer according to the incident optical image, and the electrostatic charge is reproduced by toner development or potential reading. For example, it is described in JP-A-1-290366 and JP-A-1-289975.
Further, the charge retention layer in the above method is a thermoplastic resin layer, electrostatic charges are recorded on the surface of the thermoplastic resin layer and then heated to form a frost image on the surface of the thermoplastic resin layer, thereby recording the electrostatic charge. A method for visualizing the image is described in, for example, Japanese Patent Laid-Open No. 3-192288.

Further, the present applicants have used the polymer-dispersed liquid crystal layer as the information recording layer in the above-mentioned information recording medium, and like the above, it is exposed when a voltage is applied, and the liquid crystal layer is aligned by an electric field formed by an optical sensor. The information recording / reproducing method is described in Japanese Patent Application No. 4-3
394, Japanese Patent Application No. 4-24722, Japanese Patent Application No. 5-266
Filed as No. 646. This information recording / reproducing method can visualize recorded information without using a polarizing plate.

[0004]

The layer thicknesses of the liquid crystal recording medium and the optical sensor are about 6 μm and 10 μm, respectively, and the layer thickness of the entire integrated information recording medium is very thin, less than 20 μm. For example, there has not yet been proposed an apparatus in which such a recording medium is loaded in a camera or the like so that the user can easily take a picture. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a packaging-integrated information recording medium in which recording media are integrated in a disk shape and can be incorporated in a camera or the like.

[0005]

The above object can be achieved by the present invention described below. That is, the present invention is an optical sensor in which a liquid crystal recording medium in which liquid crystal is dispersed and fixed in a resin is laminated on a first electrode layer, and a second electrode layer and a photoconductive layer are formed on a transparent substrate. And a liquid crystal recording layer and a photoconductive layer are opposed to each other, or a plurality of layers are formed in a radial shape on a disk substrate with a hole formed in the center of a single unit type information recording medium that is laminated directly or with an intermediate layer interposed. The packaging-integrated information recording medium is rotatably housed in a housing case having a window opened and closed by a shutter. Further, the present invention is a packaging-integrated information recording medium in which an address information recordable area is formed in a non-image part area of the rectangular-shaped integrated information recording medium. Further, the present invention is a packaging-integrated information recording medium, wherein an area in which address information can be recorded is formed on the back side of a base material on which the rectangular-shaped integral information recording medium is formed. Further, the present invention is a packaging-integrated information recording medium, wherein an area capable of recording photographic information is formed in a non-image portion area of the rectangular-shaped integrated information recording medium.
Further, the present invention is a packaging-integrated information recording medium, wherein an overcoat layer is provided between the first electrode layer and the liquid crystal recording layer.

[0006]

A packaging-integrated information recording medium of the present invention comprises a liquid crystal recording layer in which a liquid crystal recording layer in which a liquid crystal is dispersed and fixed in a resin is laminated on a first electrode layer, and a second electrode layer on a transparent substrate. , A photosensor having a photoconductive layer formed thereon is laminated directly or with an intermediate layer interposed so that the liquid crystal recording layer and the photoconductive layer face each other, and an integral type information recording medium is formed into a rectangular shape and a hole is formed in the center thereof. A plurality of discs are radially formed on the disc substrate and are rotatably accommodated in the case.When the image exposure and reading are performed, the window is opened and closed by the shutter and the image exposure and the reading are performed on the disc substrate through the window. By rotating and stopping the disk substrate, a plurality of image exposures and readings are performed one after another. Further, in the packaging-integrated information recording medium of the present invention, an address information recordable area is formed in a non-image part area of the rectangular-shaped integrated information recording medium, and the address information recording area is formed in the area. Recording is done. In the packaging-integrated information recording medium of the present invention, an area in which address information can be recorded is formed on the back side of the base material on which the rectangular-shaped integrated information recording medium is formed. The address information is recorded at. Further, in the packaging-integrated information recording medium of the present invention, a photographic information recordable area is formed in a non-image part area of the rectangular-shaped integrated information recording medium, and the photographic information is recorded in the area. Recording is done. The packaging-integrated information recording medium of the present invention is provided with an overcoat layer between the first electrode layer and the liquid crystal recording layer, and has durability.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a diagram showing the structure (part 1) of an integrated information recording medium of the present invention. In FIG. 1 and FIG. 2 that follow, the arrangement configuration on the plane will be mainly described (see FIG. 3, FIG. 9 and the like described later for the layer configuration). In FIG. 1, reference numeral 1 denotes a substrate, which is made of a material such as glass or plastic and has a disk shape, and has a hole formed at the center. An image forming unit 2 includes three image areas of three primary colors R, G, and B, and a plurality of image forming units are radially provided around the holes of the substrate 1. Reference numeral 3 denotes a first electrode layer, which is the image forming portion 2
Is provided on the liquid crystal recording layer and the terminal is led to the hole of the substrate 1. A light reflecting layer 4 is provided on any surface between the liquid crystal recording layer and the photoconductive layer in order to monitor the transmittance of the liquid crystal recording layer. A second electrode layer is formed on the opposite side of the light reflecting layer 4 with the photoconductive layer in between. Reference numeral 5 denotes a third electrode layer, which is provided on the liquid crystal recording layer in a region for recording information such as address information and photographing information other than the image, and the terminals are led to the outer peripheral portion of the substrate 1.

FIG. 2 is a diagram showing the structure (part 2) of the integrated information recording medium of the present invention. In FIG. 2, reference numeral 6 denotes a second electrode layer, which is provided on the substrate 1 in the region of the image forming portion 2 and the light reflection layer 4 and has terminals led to the outer peripheral portion of the substrate 1. Reference numeral 7 denotes a current monitor electrode for monitoring the dark current in the photoconductive layer or the recording current value of the darkest portion in image recording. 8 is a fourth electrode layer,
It is provided below the area for recording information such as address information and shooting information other than the image, and the terminals are led to the outer peripheral portion of the substrate 1. The address information is position information on the substrate of the integrated information recording medium on which the image is captured or captured. Address information can be written before shooting or each time shooting is performed, and the unrecorded area can be searched and the number of remaining imageable areas can be known from the information. The shooting information is information such as the shooting date and time, the place, the comment, the voice information, and the like, and includes various information associated with the image that identifies the shot image.

FIG. 3 is a view showing a cross section of the integrated information recording medium of the present invention. 3A shows a cross section taken along AA ′ in FIG. 1, FIG. 3B shows a cross section taken along BB ′ in FIG. 2, and FIG. 3C shows a cross section taken along CC ′ in FIG. 3D is a cross section taken along the line DD ′ of FIG.
(E) shows a cross section at EE 'in FIG. FIG.
As shown in (A), the third electrode layer 5 has a third electrode terminal 9
Thus, it goes around the peripheral portion of the substrate and conducts electricity to the back side of the substrate. The light reflection layer 4 is composed of the liquid crystal recording layer 22 and the photoconductive layer 21.
Is formed between. As shown in FIG. 3B, the fourth electrode layer 8 wraps around the periphery of the substrate by the fourth electrode terminal 10 and is electrically connected to the back side of the substrate. As shown in FIG. 3C, the third electrode layer 5 is formed on the liquid crystal recording layer 22, and the fourth electrode layer 8 is formed between the substrate 1 and the photoconductive layer 21. As shown in FIG. 3D, the first electrode layer 3 is circulated through the hole of the substrate by the first electrode terminal 11 and is electrically connected to the back side of the substrate. In addition, the second electrode layer 6 wraps around the peripheral portion of the substrate by the second electrode terminal 12 and is electrically connected to the back side of the substrate.
As shown in FIG. 3E, the current monitoring electrode layer 7 is formed between the liquid crystal recording layer 22 and the photoconductive layer 21.

FIG. 4 is a view showing the back surface and the address bar of the substrate 1 of the integrated information recording medium of the present invention. FIG. 4 (A)
4A is an overall view, and in FIG. 4A, reference numeral 14 is an address bar having a positioning mark and address information when the disk-shaped integrated information recording medium is rotated around a center hole and stopped. In addition, FIG. 4B shows the address bar 1
Example of configuration 4 (example in which the number of image forming units is 16 or less)
FIG. As shown in FIG. 4 (B), the address bar 14 is composed of eight element parts (corresponding to information of 1 Byte) of ~, and in the example shown in FIG. 4 (A),
Assign ~ to address information (4 bits),
(4 bits) is assigned to the positioning mark. The predetermined information is expressed by "0" and "1", and is given as a pattern to the element parts ~. For example, “0” and “1” can be distinguished by the difference in light reflectance, color, interference and the like. In addition to the optical pattern, a magnetic recording layer may be provided to form a magnetic recording pattern. In addition,
The number of the element parts of the address bar is not limited to the above eight, and a necessary number can be provided according to the number of sets of the image forming units.

FIG. 5 shows another embodiment of the present invention,
In this embodiment, as shown in FIG. 5 (A), a part of the image forming portion is used as a current monitor region in which the upper electrode layer (first electrode layer) is not provided and the current monitor electrode layer 8 is used. is there. As shown in FIG. 5 (B), the current monitor electrode layer 8 is extended so as to extend below the central hole, and the current monitor electrode terminal 17 is taken out. In this embodiment, the upper electrode layer is not provided in a part of the region, and this portion is used as the current monitor electrode layer 8 and the current monitor electrode terminal 17 is taken out above or below the central hole side. Thereby, it is possible to prevent the occurrence of conduction with the electrode terminal (second electrode terminal) of the lower electrode layer. On the other hand, in the example shown in FIG. 5C, the contact 17 is provided on the surface of the disc by making the inner diameter of the liquid crystal recording layer 22 larger than the inner diameter of the hole of the substrate.

FIG. 6 is a view showing an embodiment in which the disc-shaped integrated information recording medium is packaged in a rectangular storage case. In FIG. 6, the integrated information recording medium is rotatably accommodated. The storage case 18 is provided with a shutter 19 movable in the left-right direction in the drawing, and the front surface opening 2 provided in a part of the storage case 18 is provided.
0, the back opening 23 can be opened and closed. In this example, the recording medium is stored in the storage case 18 with the front side shown in FIG. 6A as the optical sensor side and the back side shown in FIG. 6B as the liquid crystal layer side. Storage case 18
When the camera is loaded in the camera, the shutter 19 moves in the direction of the arrow in the figure, and the image forming unit, the address information recording unit, the photographing information recording unit, and the like are opened at both the front opening 20 and the rear opening 23. Thus, it is possible to record and reproduce information from the outside. In particular, the back opening is largely opened, and the electrode terminals of the image recording section, the electrode terminals of the address information recording section, the electrode terminals of the photographing information recording section, the electrode terminals for the current monitor, and the electrical connection between the external device and It is configured so that contacts can be obtained. The back surface of the shutter 19 is also configured to open and close a drive hole 24 for rotationally driving and stopping the disc-shaped integrated information recording medium.
For reproducing information, the image forming portion is exposed by moving the shutter 19 and can be read by an image sensor such as a CCD line sensor from the back surface which is the liquid crystal layer side.

FIG. 7 is a view showing the internal structure of a disc-shaped integrated information recording medium or the like which is packaged and built in a storage case. 7A shows the front surface side, and FIG. 7B shows the cross section. In FIG. 7A, there are a plurality of image forming portions 24, which are radially formed on a disk-shaped substrate. A transmittance change monitor unit 25 is provided for each of the image forming units 24, and is configured to enable control of photographing conditions by measuring transmittance. In addition, FIG. 7 (B)
As shown in FIG. 3, clean papers 26 and 27 are provided on the inner surface side of the storage case 18 so as to face the recording medium and both sides thereof are provided to prevent the recording medium from being contaminated by dust or the like. Furthermore, since the information recording layer is sensitive to dust and moisture, it is preferable to use another dustproof and moistureproof treatment together. In the information recording / reproducing apparatus for such a packaged recording medium, in both the transmissive liquid crystal recording medium and the reflective liquid crystal recording medium, image writing light is performed from the surface which is the optical sensor side,
The incident reading light is reflected from the front or back surface in the case of the transmissive type and from the liquid crystal side in the case of the reflective type when the reflective layer is provided in the intermediate layer, and the upper electrode (electrode on the liquid crystal layer) is reflected. In the case of a layer, both the writing light and the reading light are incident from the surface (optical sensor) side.

Next, a method of manufacturing the disk on disk will be described. FIG. 8 is a diagram showing a process in which the disk on the disk is processed and shaped by the manufacturing process. In FIG. 8A, an ITO (indium oxide / tin) coating is formed on a circular substrate such as glass or plastic, and the ITO coating is patterned to form a lower electrode layer (second electrode layer 6). This patterning is performed by etching using a resist, a dry mask or the like. At this time, all the lower electrode layers can be made of the same material, but other metals such as Au and Al can be partially used. In particular, a material different from that of the electrode layer is used for the electrode terminal. As a method of forming the lower electrode terminal, there are ion plating, sputtering, vapor deposition, CVD, etc. as a method of forming a thin film of a conductive material, and silver paste printing, indium as a method of forming a thick film of a conductive material. It can be performed by soldering or spot welding. After patterning and forming the lower electrode uniformly in a circular disk shape, the spinner,
The photoconductive layer is formed by a coating process such as a blade or dip spray. The formation of this photoconductive layer is not limited to the lower electrode patterning portion, but is uniformly performed on the disk.

Next, as shown in FIG. 8B, for monitoring the dark current of the photoconductive layer so as to extend to the edge of the disc disk so as to partially overlap with the lower electrode on which the photoconductive layer is formed. The current monitor electrode 7 is laminated. This stacking method is performed by a method such as a dry mask. Next, after laminating a transparent intermediate layer, as shown in FIG. 8C, a reflective layer 42 for a transmittance monitor is formed. In addition, for the lamination of the intermediate layer, an aqueous resin and gelatin are laminated by a spinner, a blade, a dip, a spray, etc., and an inorganic insulating layer (SiO2,
Al2O3, ZnS, etc.) is laminated by vapor deposition, sputtering, ion plating, CVD, or the like. The reflective layer for transmittance monitor is made of Au, Al, ... By vapor deposition sputter ion plating or the like. Thus, FIG.
As shown in (C), an intermediate layer is laminated, a transmittance monitor reflection layer is formed, and then a liquid crystal recording layer is laminated.

Next, as shown in FIG. 8D, the upper electrode (first electrode layer 3) is patterned using a dry mask or the like so that this electrode also extends to the disk edge. In this way, a circular disk is stored in the storage case as shown in FIG. 6 to form a recording medium incorporated in a camera or the like. That is, as shown in FIG. 8E, the recording medium is rotatably supported by the rotary support 57 of a device such as a camera, and in this embodiment, the upper electrode terminal, the lower electrode terminal, and the current monitor electrode terminal. , And the address information recording terminal can be taken out from the back side of the disk-shaped substrate.

[Optical Sensor and Information Recording Medium] Next, the optical sensor and the information recording medium in the present invention will be described.
The optical sensor 29 and the information recording medium 30 are laminated in close contact with each other, and a voltage is applied in a direction substantially perpendicular to their surfaces. FIG. 9 is a diagram showing a case where the planar optical sensor 29 and the information recording medium 30 are laminated in close contact with each other in the package type information recording medium of the present invention. In FIG. 9, 3
Reference numeral 1 is a dielectric layer (intermediate layer) used in the case of laminating closely.
Is. Further, FIG. 9A shows a case where the overcoat layer 37 is not used and also shows a voltage application method. On the other hand, FIG. 9B shows a case where the overcoat layer 37 is used, and also shows a method of forming the current monitoring electrode 38. Materials, configurations, functions, etc. of the overcoat layer 37 and other layers will be described later.

The photoconductive layer of the photosensor of the present invention may be composed of a single layer or a laminated body composed of a plurality of layers. Here, a laminated photosensor will be described. In FIG. 9, 1 is a substrate, 6 is a second electrode layer,
21 is a photoconductive layer. The photoconductive layer 21 is composed of 32 charge generation layers and 33 charge transport layers. That is, the optical sensor 29 includes the substrate 1, the second electrode layer 6, and the charge generation layer 3.
2 and the charge transport layer 33. Further, 3 is a first electrode layer, 37 is an overcoat layer, and 22 is a liquid crystal recording layer, and the information recording medium 30 is constituted by these.

The operation of the configuration shown in FIG. 9 will be described. When the shutter is opened by the control circuit, the light passing through the lens from the subject reaches the three-color separation optical system, and the three colors (Red, G
reen, Blue) (not shown). The image of the subject is formed on the surface of the photoconductive layer 21 through the transparent substrate 1 and the second electrode layer 6. The photoconductive layer 21 has photoconductivity, and the conductivity is exhibited according to the light amount of each part of the formed image. That is, the light image is converted into a conductive image. A voltage is applied between the first electrode layer 3 and the second electrode layer 6 by the voltage applying means. In the power supply 34, one electrode terminal is grounded, and this ground terminal is connected to the first electrode layer 3 of the information recording medium 30 through the ground. The other electrode terminal is connected to the second electrode layer 6 of the optical sensor 29 via the switch 35 whose opening and closing is controlled by the control circuit. A resistor 36 is connected between the first electrode layer 3 and the second electrode layer 6, and when the switch 35 is open, the accumulated charge between the electrodes passes through the resistor 36 and is discharged. Therefore, there is no potential difference between both electrodes.

When the switch 35 is closed and a predetermined voltage is applied in the state where the light image is converted into the conductive image, a current flows according to the conductivity of the photoconductive layer 21. This is called a photoinduced current, and one of the features is that the photoconductive layer in the present invention has a remarkable effect of amplifying the photoinduced current. The photoinduced current causes the liquid crystal recording layer to be oriented and changes from a light scatterer to a light transmitter. When the control circuit stops applying the voltage after applying the predetermined voltage for a predetermined time, the alignment function is maintained by the memory function of the liquid crystal recording layer 22. That is, the formed image is recorded as a difference in the light scattering state of the liquid crystal recording layer 22.

[Structure and Material of Optical Sensor] Next, the structure and material of the optical sensor of the present invention will be described. The charge generation layer 32 of the optical sensor includes a charge generation material and a binder. As the charge-generating substance, a pyrylium dye,
Azurenium dye, squarylium salt dye, phthalocyanine pigment, perylene pigment, polycyclic quinone pigment,
Indigo pigments, pyrrole pigments, azo pigments, and other dyes and pigments can be used alone or in combination. As the binder, for example, polycarbonate resin, vinyl formal resin, vinyl acetal resin, vinyl butyral resin, polyester resin,
Acrylic resins, methacrylic resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins and the like can be mentioned, and binder resins can be used alone or in combination of two or more.

The mixing ratio of the charge generating agent and the binder is such that the binder is 0.1 to 1 part by weight of the charge generating agent.
It is desirable to use 10 parts by weight, preferably 0.2 to 1 part by weight. The charge generation layer has a thickness after drying of 0.01 to 1 μm, preferably 0.1 to 0.5 μm.
m is preferable, and such a film thickness shows good sensitivity and image quality. In addition, the above-described charge-generating substance that can be vapor-deposited can be formed into a film alone without using a binder.

The charge transport layer 33 comprises a charge transport material and a binder. The charge-transporting substance is a substance having a good property of transporting charges generated in the charge-generating layer, and examples thereof include oxazole-based, thiazole-based, triphenylmethane-based, styryl-based, stilbene-based, hydrazone-based, carbazole-based, enamine-based, There are aromatic amine-based, triphenylamine-based, butadiene-based, polycyclic aromatic compound-based, biphenyl-based, etc., and it is necessary to use a substance having good hole transport properties.

As the binder, the same binders as those in the charge generation layer described above, and styrene resin, styrene-butadiene copolymer resin, polyarylate resin, and phenoxy resin can be used, but preferably styrene resin and styrene-butadiene copolymer are used. Polymer resins and polycarbonate resins. The binder is 0.1 to 10 parts by weight, preferably 0.
It is desirable to use it in a ratio of 1 to 1 part by weight. The thickness of the charge transport layer after drying is from 1 to 50 μm, preferably from 3 to 26 μm. With such a thickness, good sensitivity and image quality can be obtained.

The second electrode layer 6 needs to be transparent if the information recording medium is opaque, but may be either transparent or opaque if the information recording medium is transparent.
A material that stably gives a specific resistance of 10 ⁶ Ω · cm or less, for example, a metal thin film conductive film of gold, platinum, zinc, titanium, copper, iron, tin, tin oxide, indium oxide, zinc oxide, titanium oxide, oxide A metal oxide conductive film such as tungsten or vanadium oxide, an organic conductive film such as a quaternary ammonium salt, or the like can be used alone or as a composite material of two or more kinds. Of these, oxide conductors are preferable, and indium tin oxide (ITO) is particularly preferable.

The second electrode layer 6 is formed by vapor deposition, sputtering,
It is formed by a method such as CVD, coating, plating, dipping, and electric field 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.
0 to 300 nm, the entire surface between the information recording layer,
Alternatively, it is formed according to an arbitrary pattern. Also,
It is also possible to stack two or more kinds of materials and use them.

The substrate 1 is required to have transparency if the information recording medium described later is opaque, but if the information recording medium is transparent, it may be transparent or opaque, and may be a card, a film, It has a shape of a tape, a sheet, a disk, etc. and strongly supports the optical sensor. For example, a flexible plastic film, a plastic sheet such as glass, polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polymethyl acrylate, polyester, polycarbonate, or a rigid body such as a card is used. In addition, on the other surface of the substrate where the electrodes are provided,
If the electrode is transparent, if necessary, a layer having an antireflection effect is laminated, or a transparent substrate is adjusted to a film thickness capable of exhibiting an antireflection effect, or by combining both, antireflection property is imparted. Good to do.

The photoconductive layer contains an electron-accepting substance, a sensitizing dye,
Antioxidants, ultraviolet absorbers, light stabilizers and the like may be added. The electron-accepting substance and the sensitizing dye have the functions of adjusting the base current, stabilizing the base current, and sensitizing. Each is added in an amount of 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, relative to 1 part by weight of the photoconductive substance. If less than 0.001 parts by weight, no action is shown, and 1
If the amount is more than 0 parts by weight, the image quality is adversely affected. This is the end of the description of the configuration and materials of the optical sensor of the present invention.

[Fabrication of Laminated Photosensor] Next, a method of fabricating the laminated photosensor will be described. An ITO film having a sheet resistance of 80 Ω / □ and a film thickness of 100 nm was formed by sputtering on a sufficiently washed glass substrate having a thickness of 1.1 mm to obtain an electrode. Scriber cleaning machine for electrodes (trade name: plate cleaner model 602 Ultratech)
At this point, the cleaning treatment was performed twice: pure water spraying 2 seconds, scriber cleaning 20 seconds, pure water rinsing 15 seconds, water removal by high speed rotation 25 seconds, and infrared drying 55 seconds. 3 parts by weight of a bisazo pigment having a structure shown in Table 1 below as a charge generating substance on the electrode, a vinyl chloride-vinyl acetate mixed resin (Denka vinyl # 1000D manufactured by Denki Kagaku Kogyo and 18,325.89J vinyl acetate resin manufactured by Aldrich). With 7
1 part by weight of a mixture of 5:25), 98 parts by weight of 1,4-dioxane and 98 parts by weight of cyclohexanone, and sufficiently kneaded by a mixer to prepare a coating solution, which is spinner at 1400 rpm for 0.4 seconds. Coated with.

[0030]

Embedded image After that, a film is formed on the surface of the coating film, and leveling drying is performed by leaving it in a dust-free state until the surface does not adhere, and then dried at 100 ° C. for 1 hour to form a charge generation layer having a film thickness of 300 nm. Were laminated.

On the charge generation layer, a butadiene derivative having a structure shown in Table 2 below as a charge transporting substance (T manufactured by Anan) was used.
─405) 50 parts by weight and 10 parts by weight of styrene-butadiene copolymer resin (Clearene 730L manufactured by Denki Kagaku Kogyo Co., Ltd.) are uniformly dissolved in 68 parts by weight of chlorobenzene and 136 parts by weight of 1,1,2-trichloroethane to obtain a coating solution. And

[0032]

Embedded image Using the coating solution, a spinner was used at 350 rpm,
After coating for 4 seconds, the film is formed on the surface of the coating film and left to stand without wind for leveling and drying until the surface of the coating film does not adhere. A photosensor of the present invention having a 20 μm-thick photoconductive layer including a charge generation layer and a charge transport layer was manufactured by laminating a transport layer, and was aged for 3 days in a dark place at room temperature and a relative humidity of 60% or less. .

[Structure and Material of Information Recording Medium] Next, the structure and material of the information recording medium 30 will be described. First,
Examples of the information recording medium in the present invention include a case where the information recording layer is a liquid crystal recording layer. Liquid crystal recording layer 22
Has a structure in which resin particles are dispersed in the liquid crystal phase,
As the liquid crystal material, smectic liquid crystal, nematic liquid crystal, cholesteric liquid crystal, or a mixture thereof can be used. As a liquid crystal, from the viewpoint of so-called memory property, which retains its orientation and retains information permanently,
Preference is given to using smectic liquid crystals.

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 terminal carbon group of a substance exhibiting liquid crystallinity, a fluorine type or the like, a ferroelectric substance Examples thereof include a liquid crystal substance exhibiting a smectic C phase used as a liquid crystal, a liquid crystal substance exhibiting smectic H, G, E, F and the like.

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

The liquid crystal material and the resin may be used in such a manner that the liquid crystal content is 10 to 90% by weight, preferably 40 to 80% by weight.
If it is less than 10 parts by weight, the light transmittance is low even if the liquid crystal phase is aligned by information recording, and if it exceeds 90 parts by weight, phenomena such as seeping out of the liquid crystal occur and image unevenness is not preferable. Since the film thickness of the information recording layer affects the resolution,
Film thickness after drying 0.1 μm to 10 μm, preferably 3 μm
The thickness may be 8 μm, and the operating voltage can be lowered while maintaining high resolution. If the film thickness is too thin, the contrast of the information recording portion will be low, and if it is too thick, the operating voltage will be high, which is not preferable.

Next, the overcoat layer 37 will be described. The overcoat layer 37 is provided between the first electrode layer 3 and the liquid crystal recording layer 22 as shown in FIG. 9 (B). By providing this overcoat layer 37, it is possible to further prevent the phenomenon of liquid crystal bleeding from the surface of the liquid crystal recording layer 22 and to increase the hardness of the surface of the information recording medium, thus providing durability. . As a material for forming the overcoat layer 37, for example, a resin such as polyethylene terephthalate resin, polypropylene resin, polyester resin, polystyrene resin, acrylic resin, methacrylic resin, or an ultraviolet curable resin such as acrylic acid ester or methacrylic acid ester or epoxy resin is used. A thermosetting resin such as silicone resin can be used. In addition, water-soluble resins having low compatibility with organic solvents, such as polyvinyl alcohol, water-based polyurethane, and water glass, and fluorine-based resin CYTOP (Asahi Glass Co., Ltd.)
Manufactured) can be used.

In particular, when the ultraviolet curable resin is used, the phenomenon such as bleeding on the surface of the information recording medium is suppressed, the image is disturbed by the bleeding of liquid crystal onto the surface of the information recording medium, and the conductivity of the electrode layer is lowered. Can be prevented. In addition, the surface hardness can be made extremely high, image disturbance due to damage to the information recording medium on the surface of the information recording medium and damage to the information recording medium can be prevented, and durability can be improved. Further, it is possible to prevent image deterioration due to cracking of the transparent electrode layer laminated on the surface of the information recording medium. Overcoat layer 37 is 0.1-20 μ
m, preferably 0.3-5 μm, more preferably 0.
It is preferable that the thickness is 5 to 2 μm. This is the end of the description of the configuration and materials of the information recording medium of the present invention.

[Production of Information Recording Medium] Next, a method for producing the information recording medium will be described. An intermediate layer, which will be described later, is provided on the disk-shaped optical sensor obtained by the above-mentioned "production of laminated optical sensor", and a polyfunctional monomer (dipentaerythritol hexaacrylate, manufactured by Toagosei Kagaku) , M-400) 40 parts by weight, a photocuring initiator (2
-Hydroxy-2-methyl-1-phenylpropane-1
-ON, 2 parts by weight of Ciba-Geigy, Darocur 1173), 50 parts by weight of liquid crystal (90% of smectic liquid crystal (Merck S-6), 10% of nematic liquid crystal (Merck E31LV)), Surfactant (Sumitomo 3M, Florard FC-430) 3 parts by weight Coating solution obtained by uniformly dissolving in 96 parts by weight of xylene
After coating using a blade coater with a gap of 0 μm, dry at 47 ° C. for 3 minutes, then 47 ° C.
Was dried under reduced pressure for 2 minutes, and the coating film was immediately cured by irradiation with infrared rays of 0.3 J / cm ² to obtain an information recording medium having an information recording layer with a film thickness of 6 μm. Liquid crystal was extracted from the information recording layer surface using hot methanol and dried, and then 1000 with a scanning electron microscope (S-800 manufactured by Hitachi, Ltd.).
When observing the internal structure by a factor of 2, the layer surface is 0.6 μm.
It had a structure in which a resin particle phase having a particle diameter of 0.1 μm was filled in a liquid crystal phase which was covered with an ultraviolet curable resin and which formed a continuous layer inside the layer.

[Structure and Material of Integrated Type Intermediate Layer] As described above, in the structure of the integrated type information recording medium, the optical sensor and the information recording medium are arranged so as to face each other with the dielectric layer 31 interposed therebetween and are directly laminated. It is a figure. The configuration via the dielectric layer 31 is particularly suitable when the photoconductive layer in the photosensor is formed by coating using a solvent, and if the information recording layer is directly formed by coating on the photoconductive layer, they are mutually formed. The liquid crystal in the information recording layer is eluted by the action, and the image unevenness due to the elution of the photoconductive material by the solvent for forming the information recording layer can be prevented, and the optical sensor and the information recording medium are integrated. Is possible.

When forming the dielectric layer 31, it is necessary that the dielectric layer 31 is insoluble in neither the photoconductive layer forming material nor the information recording layer forming material, and it is necessary that it is not conductive. Is. In the case of having conductivity, the space charge is diffused and the resolution is deteriorated, so that the insulating property is required. Further, the dielectric layer lowers the distribution voltage applied to the liquid crystal layer or deteriorates the resolution. Therefore, it is preferable that the film thickness is thin, preferably 2 μm or less. In addition to the generation of image noise due to various interactions, there is a problem of penetration due to defects such as pinholes in the multilayer coating. The penetrability due to defects such as pinholes depends on the solid content ratio of the material to be laminated and coated, the type of solvent, and the viscosity, so the film thickness of the laminated coating is set appropriately, but at least 10 μm
The following film thickness is preferable, and 0.1 μm to 3 μ is preferable.
It is good to set m. Further, in consideration of the voltage distribution applied to each layer, it is preferable to use a material having a high dielectric constant as well as a thin film.

As a material for forming the dielectric layer 31, inorganic materials such as SiO ₂ , TiO ₂ , CeO ₂ , and Al are used.
₂ O ₃ , Si ₃ N ₄ AiN, TiN, MgF ₂ , Zn
When S, a combination of silicon dioxide and titanium dioxide, a combination of zinc sulfide and magnesium fluoride, a combination of aluminum oxide and germanium, and the like are used and laminated by a vapor deposition method, a sputtering method, a chemical vapor deposition (CVD) method, or the like. Good. Alternatively, a water-soluble resin having a low compatibility with an organic solvent, for example, an aqueous solution of polyvinyl alcohol, water-based polyurethane, water glass, or the like may be used and 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 fluororesin which can be applied, for example, the fluororesin disclosed in JP-A-4-24728,
Furthermore, organic materials such as polyparaxylylene and polyvinyl alcohol, which are film-formed in a vacuum system, can be preferably used. As described above, as the information recording medium, the recording by the information exposure is visualized by the orientation of the liquid crystal, but by selecting the combination of the liquid crystal and the resin, the information once oriented and the visualized information is not erased, It is possible to impart sex. Further, by heating to a high temperature near the isotropic phase transition, the memory property can be erased, so that it can be used for information recording again. This is the end of the description of the configuration and material of the intermediate layer of the integrated type according to the present invention.

[Temperature Characteristics of Information Recording Medium] Next, the temperature characteristics of the information recording medium used in the present invention will be described.
FIG. 10 is a diagram showing an example of temperature characteristics of the information recording medium used in the present invention. In FIG. 10, the horizontal axis represents the voltage (Volt) applied to the liquid crystal recording layer 22, and the vertical axis represents the modulation rate (%). The modulation rate is a scale in which the output of the detector in the maximum light transmission state is 100% and the output of the detector in the maximum light scattering state is 0% when optically reading the recorded information from the information recording medium. Is given to the output of the detector. As shown in the figure, the reason why the modulation rate changes sharply with respect to the change in voltage is
It shows that the sensitivity is extremely high. On the other hand, the change in the characteristic of the modulation rate with respect to temperature indicates that the temperature and voltage are controlled when used in an environment where the temperature changes. It also shows that it is possible to erase the recorded information by utilizing such characteristics. In the present invention, in consideration of such characteristics of the information recording medium, specific settings such as a temperature condition and a voltage condition during use are set.

[Photo-induced Current Amplifying Action of Photo Sensor] Next, the photo-induced current amplifying action of the photo sensor 29, which is one of the features of the present invention, will be described. When the light pattern is applied to the light sensor, the light sensor exhibits conductivity, and the voltage applied to the information recording medium or the amount of charge applied is amplified over time. Further, if the voltage is continuously applied even after the light irradiation is finished, the photosensor maintains the expressed conductivity in a relaxation-attenuating manner, and the voltage applied to the information recording medium or the applied charge amount continues to elapse. Is amplified. Then, these voltages and charge amounts form a voltage pattern and charge amount pattern having the same shape as the light pattern applied to the optical sensor, and are further medium-converted into a visible pattern or the like as necessary and recorded on the information recording medium. It

The time-dependent amplifying action of the applied charge amount in the photosensor, that is, the "photoinduced current amplifying action" will be described in more detail. An optical sensor and a measuring device are configured as follows, and the photo-induced current amplification action of the optical sensor is measured. An ITO electrode is provided on transparent glass, a photoconductive layer is formed on the electrode, and 0.16 cm is further formed on the photoconductive layer.
Form ² gold electrodes. Then, between the two electrodes, ITO
While applying a constant DC voltage with the electrode as a positive electrode,
0.5 seconds after the start of voltage application, light is irradiated from the substrate side for 0.033 seconds, and the behavior of the current value in the photosensor during the measurement time is measured from the start of light irradiation (t = 0). The irradiation light is a xenon lamp (L2274 manufactured by Hamamatsu Photonics).
To the light source, a green filter having characteristics shown in FIG. 11 (manufactured by Nippon Vacuum Optical Co., Ltd.) was used to select and irradiate green light, and the irradiation light intensity was measured with an illuminometer (manufactured by Minolta Co., Ltd.) to obtain 20 lux To do.

Considering the power spectrum of the light source, the light transmittance of the transparent substrate, the ITO film, and the spectral characteristics of the filter when light is irradiated at this light intensity, the photoconductive layer has 4.2 × 10 5.
¹¹ photons / cm ² seconds are incident. Then, if all the incident photons are converted into photocarriers, theoretically, the photocurrent is 1.35 × 10 ⁻⁶ A / unit area.
A current of cm ² is generated.

Here, in the case of the photo-induced current actually generated by the optical sensor with respect to the theoretical photo-current when measured by the measuring device (photo-induced current value actually generated by the photo-sensor / theoretical The photocurrent value) is defined as the quantum efficiency of the photosensor. The photo-induced current is the current value of the light irradiation part minus the base current value which is the current that flows in the part when light is not irradiated. It refers to a current that flows due to it and is different from so-called photocurrent. The photoinduced current amplification action in the photosensor of the present invention is defined as such behavior of photoinduced current.

An optical sensor having a photo-induced current amplifying action and an optical sensor having no photo-induced current amplifying action (hereinafter referred to as a comparative sensor) according to the present invention will be described by using the measurement results of the measuring device. First, the measurement result of the comparative sensor is shown in FIG. In FIG. 12, line (m) is a reference line indicating the theoretical value (1.35 × 10 ⁶ A / cm ² ), and light irradiation was performed for 0.033 seconds, and voltage application was continued after light irradiation. Indicates. The line (n) is the actual measurement line of the photosensor having no photoinduced current amplification effect, and the change in quantum efficiency during light irradiation is shown in FIG.

On the other hand, in the photosensor of the present invention, as shown in FIG. 14 as an example, the photoinduced current increases at the time of light irradiation, and as is clear from FIG. It can be seen that the quantum efficiency exceeds 1 in 0.01 seconds and continues to increase thereafter. Further, in the comparative sensor, the photocurrent abruptly attenuates at the same time as the light irradiation is completed, so that even if the voltage is continuously applied after the light irradiation, the effective current as the light information cannot be obtained. On the other hand, in the photosensor of the present invention, the photoinduced current continuously flows by continuing the voltage application even after the light irradiation, and the photoinduced current can be continuously taken out, and the optical information can be continuously obtained. it can. This completes the description of the organic current amplification function of the photosensor of the present invention.

[Semiconductivity of Optical Sensor] In the optical sensor of the present invention, the photoconductive layer is a semiconductive material in the dark.
From the flowing current density, the specific resistance in the dark is 10 ⁹ to 10 ¹³ Ω.
It is preferably cm. Particularly, the specific resistance is 10 ¹⁰ to 1
With 0 ¹¹ Ω · cm, the amplification effect is remarkable. In the case of an optical sensor having a specific resistance larger than 10 ¹³ Ω · cm, 10 ⁵ to 1
In the electric field strength range of 0 ⁶ V / cm, it does not exhibit the amplifying action as the optical sensor of the present invention. Also, the specific resistance is 10 ⁹ Ω · c.
If the photosensor is less than m, a large amount of current flows, and noise is likely to occur due to the current, which is not preferable.

On the other hand, for an organic photoconductor used for general electrophotography, a material having a dark specific resistance of 10 ¹⁴ to 10 ¹⁶ Ω · cm is used as an insulating material in the dark. Has been. Therefore, when the photosensor of the present invention is used in electrophotography, the purpose of electrophotography cannot be achieved.
Further, the organic photoreceptor used in general electrophotography cannot attain the object of the present invention when used in the photosensor of the present invention.

If the information recording layer of the information recording medium is a liquid crystal recording layer, it is necessary to set the sensitivity of the optical sensor in the operating voltage region of the liquid crystal. That is, the contrast voltage, which is the voltage between the voltage (bright potential) applied to the information recording medium in the maximum exposure portion and the voltage (dark potential) applied to the information recording medium in the minimum exposure portion,
It is necessary that the liquid crystal recording layer in the information recording medium be included in the operating voltage region and have a size capable of obtaining a predetermined operating amplitude. Therefore, for example, the dark potential applied to the liquid crystal layer of the minimum exposure portion of the photosensor needs to be set to about the operation start potential of the liquid crystal. Therefore, the resistivity of the information recording medium is 10 ¹⁰ to 10 ¹³ Ω · cm at room temperature, which is 1
With an electric field of 0 ⁵ to 10 ⁶ V / cm applied, 10
The conductivity is required to the extent that a base current of ⁻⁴ to 10 ⁻⁷ A / cm ² is generated, and the range of 10 ⁻⁵ to 10 ⁻⁶ A / cm ² is preferable.

In the photosensor having a base current of less than 10 ^-7 A / cm ² , the liquid crystal recording layer layer is not oriented even in the maximum exposure state, and in the photosensor having a base current of 10 ^-4 A / cm ² or more, the liquid crystal layer is not aligned. Even in the minimum unexposed state, a large current flows at the same time as voltage is applied, and the liquid crystal recording layer is oriented. Therefore, even if exposed, a difference in transmittance depending on the exposure amount cannot be obtained. Further, since the operating voltage and range may vary depending on the type of liquid crystal, it is necessary to consider the voltage distribution in the information recording medium when setting the applied voltage and the voltage application time. This is the end of the description of the semiconductivity of the optical sensor of the present invention.

[0055]

As described above, according to the present invention,
It is possible to provide a packaging-integrated information recording medium in which recording media are integrated in a disk shape and can be incorporated into a camera or the like, and high sensitivity is achieved by using an optical sensor having a photo-induced current amplification effect, High resolution recording can be performed by combining the optical sensor and an information recording medium having a liquid crystal recording layer as a constituent element. The packaging-integrated information recording medium of the present invention includes a liquid crystal recording medium in which a liquid crystal recording layer in which a liquid crystal is dispersed and fixed in a resin is laminated on a first electrode layer, a second electrode layer on a transparent substrate, and an optical layer. A disk in which a photosensor having a conductive layer and a liquid crystal recording layer and a photoconductive layer are laminated so as to face each other directly or with an intermediate layer interposed to form a rectangular unitary information recording medium and a hole is formed in the center thereof. It is formed in a radial pattern on the board and is rotatably housed in the case.
Image exposure and reading are performed on the disk substrate through the window by opening and closing the window with a shutter, and a plurality of image exposures and readings can be performed one after another by rotating and stopping the disk substrate. Further, in the packaging-integrated information recording medium of the present invention, an address information recordable area is formed in a non-image part area of the rectangular-shaped integrated information recording medium, and the address information recording area is formed in the area. Records can be made. In the packaging-integrated information recording medium of the present invention, an area in which address information can be recorded is formed on the back side of the base material on which the rectangular-shaped integrated information recording medium is formed. Address information can be recorded in the. Further, in the packaging-integrated information recording medium of the present invention, a photographic information recordable area is formed in a non-image part area of the rectangular-shaped integrated information recording medium, and the photographic information is recorded in the area. Records can be made. Further, the packaging-integrated information recording medium of the present invention is provided with the overcoat layer between the first electrode layer and the liquid crystal recording layer, so that durability can be obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing a part (1) of the configuration of an integrated information recording medium of the present invention.

FIG. 2 is a diagram showing a part (2) of the configuration of the integrated information recording medium of the present invention.

FIG. 3 is a diagram showing a cross section of an integrated information recording medium of the present invention.

FIG. 4 is a diagram showing a back surface of a substrate and an address bar of the integrated information recording medium of the present invention.

FIG. 5 is a diagram showing another embodiment of the present invention.

FIG. 6 is a diagram showing an embodiment in which a disc-shaped integrated information recording medium is packaged in a rectangular storage case.

FIG. 7 is a diagram showing an internal configuration of a disc-shaped integrated information recording medium or the like which is packaged and built in a storage case.

FIG. 8 is a diagram showing a process in which a disk on a disk is processed and shaped.

FIG. 9 is a diagram showing a configuration in which an optical sensor and an information recording medium are laminated in close contact with each other in the package type information recording medium of the present invention.

FIG. 10 is a diagram showing an example of temperature characteristics of an information recording medium used in the present invention.

FIG. 11 is a diagram showing characteristics of a green filter used in the present invention.

FIG. 12 is a diagram showing a measurement result of a conventional sensor that does not have a photo-induced current amplification effect unlike the photo sensor according to the present invention.

FIG. 13 is a diagram showing a change in quantum efficiency during light irradiation of an optical sensor having no photoinduced current amplification effect.

FIG. 14 is a diagram showing an increase in photoinduced current during light irradiation in the photosensor having the photoinduced current amplification effect according to the present invention.

FIG. 15 is a diagram showing the quantum efficiency of photoinduced current during light irradiation in the photosensor having the photoinduced current amplification effect according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Image forming part 3 1st electrode layer 4 Light reflection layer 5 3rd electrode layer 6 2nd electrode layer 7 Current monitoring electrode layer 8 4th electrode layer 9 3rd electrode terminal 10 4th Electrode terminal 11 First electrode terminal 12 Second electrode terminal 13 Current monitor electrode terminal 14 Address bar 15 Non-image area 16 Current monitor electrode layer 17 Current monitor electrode terminal 18 Storage case 19 Shutter 20 Surface opening 21 Photoconductive layer 22 Liquid crystal recording layer 23 Back opening 24 Drive hole 25 Transmittance change monitor 26, 27 Clean paper 27 Charge transport layer 28 Rotation support 29 Optical sensor 30 Information recording medium 31 Dielectric layer 32 Charge generation layer 33 Charge Transport layer 34 Power supply 35 Switch 36 Resistance 37 Overcoat layer 38 Current monitor electrode layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hironori Ueyama 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Within Dai Nippon Printing Co., Ltd. (72) Shinichi Sakano 1-chome, Ichigaya-Kagacho, Shinjuku-ku, Tokyo No. 1 within Dai Nippon Printing Co., Ltd. (72) Inventor Masato Okabe 1-1-1 Ichigaya Kagacho, Shinjuku-ku, Tokyo Within Dai Nippon Printing Co., Ltd.

Claims (5)

[Claims] 1. A liquid crystal recording medium in which a liquid crystal recording layer in which liquid crystal is dispersed and fixed in a resin is laminated on a first electrode layer, and an optical sensor in which a second electrode layer and a photoconductive layer are formed on a transparent substrate. Are formed in a radial pattern on a disc substrate having a hole in the center of a single unit type information recording medium in which a liquid crystal recording layer and a photoconductive layer are opposed to each other directly or with an intermediate layer interposed. A packaging-integrated information recording medium, which is rotatably housed in a housing case having a window opened and closed by a shutter. 2. A packaging-integrated information recording medium according to claim 1, wherein an address information recordable area is formed in a non-image portion area of the rectangular-shaped integrated information recording medium. . 3. The packaging according to claim 1, wherein an area in which address information can be recorded is formed on the back side of the base material on which the rectangular integrated information recording medium is formed. Integrated information recording medium. 4. A packaging-integrated information recording medium according to claim 1, wherein an area in which photographing information can be recorded is formed in a non-image portion area of the rectangular-shaped integrated information recording medium. . 5. An overcoat layer is provided between the first electrode layer and the liquid crystal recording layer.
The packaging-integrated information recording medium described.