JPH08167180A - Information recording medium integrated with package - Google Patents

Abstract

PURPOSE: To provide an information recording medium integrated with a package by forming the information recording medium in a square form on a card substrate and fixing and housing the substrate in a housing case which can be opened and closed with a shutter. CONSTITUTION: An ITO film is formed on a square substrate 1 and patterned to form a lower electrode layer 14, on which a photoconductive layer is formed by coating. Then an electrode 16 to monitor the current is deposited with partly overlapped on the electrode layer 14. Then a transparent intermediate layer comprising a dielectric material is deposited and a light-reflecting layer 19 to monitor transmittance is formed. After the intermediate layer and the reflecting layer 19 are thus formed, a liquid crystal recording layer is deposited. Then an upper electrode 15, electrode 17 to record addresses, and electrode 18 to record information about photographing are patterned to be extended to the edge part of the substrate 1. The obtd. substrate 1 is mounted on a PCB 5 and the electrodes are connected to the wiring pattern of the PCB. Then the substrate with the PCB is housed in a housing case having a window which is opened and closed with a shutter to produce a recording medium to be assembled in a camera or the like.

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 integral type formed in a rectangular shape. The present invention relates to a packaging-integrated information recording medium in which information recording media are formed in a matrix on a card substrate 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 thereof is to provide a packaging-integrated information recording medium in which the integral-type information recording medium is formed in a matrix on a card substrate and packaged.

[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 the liquid crystal recording layer and the photoconductive layer are opposed to each other directly or with an intermediate layer interposed to form an integral information recording medium into a rectangular shape and formed in a plurality of rows and columns on a card substrate, and the shutter is opened and closed. A packaging-integrated information recording medium fixedly housed in a housing case having a window. The present invention also provides a packaging-integrated information recording medium, wherein a liquid crystal transmittance monitor light reflection layer is formed in a non-image area of the rectangular-shaped integral information recording medium. The present invention also provides a current monitor electrode on the non-image area of the rectangular information recording medium formed on the opposite side of the second electrode layer of the photosensor via the photoconductive layer. A packaging-integrated information recording medium having layers formed therein. 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, on the back side of the substrate on which the integral information recording medium formed in the rectangular shape is formed,
A packaging-integrated information recording medium having an area capable of recording address information. In the present invention, in the non-image area of the integrated information recording medium formed in the rectangular shape,
It is a packaging-integrated information recording medium having an area in which photographing information can be recorded. 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. , An optical information sensor 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 the integral type information recording medium is formed into a rectangular shape and a plurality of matrix shapes are formed on the card substrate. It is fixedly stored in a storage case that has a window part that is opened and closed by a shutter.When performing image exposure and reading, the shutter is opened and closed, and image exposure and reading are performed on the card substrate through the window. By moving and stopping the card substrate, a plurality of image exposures and readings are performed one after another. In the packaging-integrated information recording medium of the present invention, a liquid crystal transmittance monitor light reflecting layer is formed in the non-image area of the rectangular information recording medium. The liquid crystal transmittance is monitored by. In the packaging-integrated information recording medium of the present invention, the photoconductive layer is interposed between the second electrode layer of the photosensor and the non-image area of the rectangular-shaped integrated information recording medium. The current monitoring electrode layer is formed on the opposite side, and the current is monitored by the current monitoring electrode layer. 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]

FIG. 1 is a view showing the external appearance of a package-integrated information recording medium of the present invention. In FIG. 1, reference numeral 1 denotes a storage case, which is made by molding an insulating material such as plastic. Reference numeral 2 denotes a connector having a large number of connection pins, which is electrically connected to a package-integrated information recording medium and an external device (for example, a camera) such as a photographing device for information communication,
Imaging control, power supply, etc. are performed. Reference numeral 3 denotes a shutter, which is opened when an image is picked up and recorded on an information recording medium or when the recording is reproduced, and the shutter is detached from the photographing device and stored.
It is closed when carried. Although the shutter 3 is shown as a sliding door that opens and closes in the horizontal direction in FIG. 1, it may be configured to be movable up and down and open and close vertically. Four
Is a handle of the shutter 3 and is a portion where an opening / closing mechanism in a photographing device or the like acts on the shutter 3. Reference numeral 5 shown by a dotted line is a PCB (printed wiring board) that supports and fixes the information recording medium and the connector, and electrically connects them.

FIG. 2 is a diagram showing the structure of a recording medium housed in the housing case. 2, the same parts as those in FIG. 1 are designated by the same reference numerals. Hereinafter, in the drawings of the present invention, the same parts are designated by the same reference numerals. Figure 2
In 6, a substrate 6 is made of a material such as glass or plastic and has a rectangular shape, and an electrode, a liquid crystal recording layer, a photoconductive layer and the like are formed on the substrate 6. Reference numeral 7 on the substrate 6 is an information recording area in which an optical pattern is recorded. The information recording areas are arranged on the substrate 6 in a plurality of rows and columns. Further, reference numeral 8 is an image forming section in which image information is recorded. In the case of a color image, the image information is recorded in parallel in three areas corresponding to the three primary colors of RGB.

FIG. 3 shows an example of a photographing device (camera) using the packaging-integrated information recording medium of the present invention. FIG. 3 (A) shows an optical system and FIG. 3 (B) shows a casing. FIG. 6 is a perspective view showing a state where a recording medium is stored in the body. FIG.
In (A), 9 is a lens for image formation, and 10 is a prism for switching the image formation position to an upper position or a lower position. Although the three-color separation optical system is not shown in FIG. 3A, it is arranged at an appropriate position between the lens 9 and the recording medium, for example, behind the prism 10. In FIG. 3B, 11 is a housing, and 12 is a connector receiver for receiving the connector 2. The connector receiver 12 stops moving in a direction indicated by an arrow by a moving means (not shown), and the information is received together with the prism 10. It is configured to select the recording area 7. Reference numeral 13 is a flexible multi-core cable connected to the connector 12, and the other end is connected to a circuit board inside the photographing device.

FIG. 4 is a diagram showing the structure of the information recording area. 4A is a plan view, and FIGS. 4B to 4D are cross-sectional views taken along line BB ′ to DD ′ in FIG. 4A.
In FIG. 4 (A), 14 is a second layer formed on the substrate 6.
The electrode layer 15 is a first electrode layer formed on the liquid crystal recording layer (described later). 16 is an electrode layer for current monitoring,
Reference numeral 17 is an address recording electrode layer, and 18 is a photographing information recording electrode layer. As shown, the second electrode layer 14 is provided below the region including all the other electrode layers. Reference numeral 19 denotes a light reflection layer, which is provided between the liquid crystal recording layer and a photoconductive layer (described later) to monitor the transmittance of the liquid crystal recording layer, and a predetermined area is covered by the first electrode layer 15. ing.

In FIG. 4B, reference numeral 20 denotes a first electrode terminal, which electrically connects the first electrode layer 15 and the wiring of the PCB 5. Reference numeral 21 is a photoconductive layer, and 22 is a liquid crystal recording layer. In FIG. 4C, a second electrode terminal 23 electrically connects the second electrode layer 14 to the wiring of the PCB 5. In FIG. 4D, reference numeral 24 denotes a current monitor electrode terminal, which electrically connects the current monitor electrode layer 16 and the wiring of the PCB 5. Address recording electrode layer 17,
The same method is used for the photographing information recording electrode layer 18
The wiring of B5 is electrically connected. The address recording electrode layer 17 is for recording address information, and the address information is position information on the substrate of the integrated information recording medium on which an image is captured or captured. Every time a picture is taken, address information can be written, and the unrecorded area can be searched and the number of remaining imageable areas can be known from the information.
The photographing information recording electrode layer 18 is for recording photographing information, and the photographing information is information such as a photographing date and time, a place, a comment, and voice information, and identifies the photographed image. Various information associated with the image is included.

FIG. 5 is a view showing an example of the back surface of the packaging-integrated recording medium of the present invention. The back surface of the packaging-integrated recording medium in FIG. 5 is covered, and the magnetic stripe 25 is provided on the back surface, so that magnetic recording can be used together. Further, the IC module 26 is incorporated so that information can be electrically written in the IC memory.
By using information recording by light, magnetism and electricity in this way, not only image information but also audio information, ID information,
It is possible to store the security information and the like in a form suitable for each. In the example of FIG. 5, since the back surface is covered, recording / reproduction of image information and the like is all performed from the direction of the front shutter.

FIG. 6 shows an example in which address marks are provided on the back surface of the substrate 5 of the packaging-integrated recording medium of the present invention, that is, the surface on which the second electrode layer 14 is not provided. Figure 6
6A is an overall view, and FIG. 6B is a partially enlarged view. The back surface of the packaging-integrated recording medium of FIG. 6 may be provided with a shutter so that it can be opened and closed like the front surface. Further, the shutter 5 may be omitted, and the back surface of the substrate 5 may be directly used as the back surface of the packaging-integrated recording medium. In FIG. 6A, 27 is an address mark. The address mark 27 is provided in a portion outside the information recording area 7 and
Is provided at a predetermined position whose relative position is accurately determined. As shown in FIG. 6B, the address mark 27
Is an address 29 for identifying a position mark 28 and a plurality of address marks 27 that can be accurately and easily read by an optical sensor (for example, consists of four element parts in the figure).
It consists of and. The address 29 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.

Next, a method of manufacturing the integrated information recording medium will be described. FIG. 7 is a flowchart showing the manufacturing process of the package-integrated information recording medium. In FIG. 7, glass,
An ITO (indium oxide / tin) film is formed on a rectangular substrate 1 made of plastic or the like, and is patterned to form a lower electrode layer (second electrode layer 14). 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,
Ion plating, sputtering, vapor deposition, CVD, etc. can be used to form a thin film of conductive material, and silver paste printing, indium soldering, spot welding, etc. can be used to form a thick film of conductive material. Can be done (S1). After the lower electrode is uniformly patterned and formed on the rectangular card substrate as described above, a photoconductive layer is then formed by a coating process such as a spinner, a blade, or a dip spray. The formation of this photoconductive layer is not limited to the lower electrode patterning portion, but is uniformly performed on the card substrate (S
2).

Next, a current monitor electrode 16 for monitoring the dark current of the photoconductive layer is laminated so as to extend to the edge portion of the card substrate so as to partially overlap with the lower electrode on which the photoconductive layer is formed. This stacking method is performed by a method such as a dry mask (S3). Next, after laminating a transparent intermediate layer made of a dielectric material (S4), the light reflection layer 1 for the transmittance monitor is formed.
9 is formed (S5). 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, Al2O
3, ZnS, etc.) are 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. In this way, the intermediate layer is laminated to form the transmittance monitor reflection layer, and then the liquid crystal recording layer is laminated (S6).

Next, the upper electrode (first electrode layer 15), the address recording electrode layer 17, and the photographing information recording electrode layer 18 are patterned using a dry mask or the like, and these electrodes are also extended to the edge of the card substrate. Make it extend (S7). The substrate 1 thus manufactured, on which electrodes, recording layers, photosensors, etc. are formed, is attached to a PCB 5 as shown in FIG.
Connect with CB wiring pattern. Then, the recording medium is stored in the storage case 1 as shown in FIG. 1 to be a recording medium to be incorporated in a camera or the like (S8). When used, as shown in FIG. 3B, it is connected to a connector receiver 12 of a device such as a camera and fixed, and the moving means of the camera sequentially records images in a plurality of image forming sections, and at the same time, the address information is recorded. , Record shooting information, etc.

[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 30 and the information recording medium 31 are laminated in close contact with each other, and a voltage is applied in a direction substantially perpendicular to their surfaces. FIG. 8 is a diagram showing a case where the planar optical sensor 30 and the information recording medium 31 are closely adhered and laminated in the package type information recording medium of the present invention. In FIG. 8, 3
2 is a dielectric layer (intermediate layer) used in the case of stacking closely
Is. Further, FIG. 8A shows a case where the overcoat layer 38 is not used and also shows a voltage application method. On the other hand, FIG. 8B shows a case where the overcoat layer 38 is used, and also shows a method of forming the current monitoring electrode 39. Materials, configurations, functions, etc. of the overcoat layer 38 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. 8, 6 is a substrate, 14 is a second electrode layer, and 21 is a photoconductive layer. The photoconductive layer 21 is composed of 33 charge generation layers and 34 charge transport layers.
That is, the photosensor 30 includes the substrate 6, the second electrode layer 14, the charge generation layer 33, and the charge transport layer 34. Further, 15 is a first electrode layer, 38 is an overcoat layer, 2
Reference numeral 2 denotes a liquid crystal recording layer, which constitutes the information recording medium 30.

The operation of the configuration shown in FIG. 8 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 6 and the second electrode layer 14. 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 15 and the second electrode layer 14 by the voltage applying means. In the power supply 35, one electrode terminal is grounded, and this ground terminal is connected to the first electrode layer of the information recording medium 31 through the ground. The other electrode terminal is connected to the second electrode layer of the optical sensor 30 via the switch 36 whose opening and closing is controlled by the control circuit. A resistor 37 is connected between the first electrode layer 15 and the second electrode layer 14, and when the switch 36 is open,
The accumulated charge between the electrodes passes through the resistor 37 and is discharged, so that no potential difference occurs between both electrodes.

When the switch 36 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. In the photosensor, the charge generation layer 33 includes a charge generation substance and a binder. Examples of the charge generating substance include pyrylium dyes, azurenium dyes, squarylium salt dyes, phthalocyanine pigments, perylene pigments, polycyclic quinone pigments, indigo pigments, pyrrole pigments, azo pigments, and other dyes and pigments. Can be used alone or in combination. Examples of the binder include polycarbonate resin, vinyl formal resin, vinyl acetal resin, vinyl butyral resin, polyester resin, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin and the like. The binder resins may 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 34 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 first electrode layer 15 is the information recording medium is required to have transparency as long as opaque, transparent if the information recording medium has a transparency may be either opaque, 10 ⁶ Omega · Material that stably gives a specific resistance of cm or less, for example, metal thin film conductive film of gold, platinum, zinc, titanium, copper, iron, tin, etc., tin oxide, indium oxide, zinc oxide, titanium oxide, tungsten oxide, vanadium oxide A metal oxide conductive film such as the above, 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 first electrode layer 15 is formed by a method such as vapor deposition, sputtering, 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 information recording. For example, the thickness of the ITO film is about 10 to 300 nm, and the entire surface between the information recording layer and Alternatively, it is formed according to an arbitrary pattern. Further, two or more kinds of materials can be laminated and used.

The substrate 6 is required to have transparency if the information recording medium described later is opaque. 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 2 will be described. First, as the information recording medium in the present invention, the information recording layer may be a liquid crystal recording layer. The liquid crystal recording layer has a structure in which resin particles are dispersed in the liquid crystal phase, and as the liquid crystal material, smectic liquid crystal, nematic liquid crystal, cholesteric liquid crystal, or a mixture thereof can be used. As the liquid crystal, it is preferable to use a smectic liquid crystal from the viewpoint of so-called memory property that retains its orientation and permanently retains information.

As the smectic liquid crystal, a liquid crystal substance exhibiting a smectic A phase such as a cyanobiphenyl type, a cyanoterphenyl type, a phenyl ester type 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 38 will be described. The overcoat layer 38 is provided between the first electrode layer 3 and the liquid crystal recording layer 22 as shown in FIG. By providing the overcoat layer 38, the phenomenon of liquid crystal seepage from the surface of the liquid crystal recording layer 22 can be further prevented, the hardness of the information recording medium surface can be increased, and durability is imparted. . As a material for forming the overcoat layer 38, 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. 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 38 is 0.1 to 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. On the card-shaped optical sensor obtained by the above-mentioned "manufacturing of laminated optical sensor",
An intermediate layer to be described later is provided, and 40 parts by weight of a polyfunctional monomer (dipentaerythritol hexaacrylate, M-400 manufactured by Toagosei Kagaku Co., Ltd.) and 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)), interface 3 parts by weight of an activator (Sumitomo 3M, Florard FC-430) was uniformly dissolved in 96 parts by weight of xylene.
After coating using a blade coater with a gap of m, it is dried at 47 ° C for 3 minutes and then at 47 ° C for 2 minutes.
The coated film was immediately dried under reduced pressure for 0.3 minutes and irradiated with 0.3 J / cm ² no infrared rays to obtain an information recording medium having an information recording layer with a thickness of 6 μm. After extracting the liquid crystal from the information recording layer surface with hot methanol and drying it, the internal structure was observed with a scanning electron microscope (S-800 manufactured by Hitachi, Ltd.) at 1000 times. 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 a cured resin and 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 32 interposed therebetween and are directly laminated. It is a figure. The structure including the dielectric layer 32 is particularly suitable when the photoconductive layer in the photosensor is formed by coating using a solvent, and when the information recording layer is directly formed by coating on the photoconductive layer, the mutual formation of these layers is prevented. 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.

In forming the dielectric layer 32, it is necessary that the dielectric layer 32 has no solubility in the photoconductive layer forming material and the information recording layer forming material, and that it has no conductivity. 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 the material for forming the dielectric layer 32, 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. 9 is a diagram showing an example of temperature characteristics of the information recording medium used in the present invention. In FIG. 9, the horizontal axis represents the liquid crystal recording layer 2
2 is a voltage (Volt) applied to 2, 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 steep change of the modulation rate with respect to the change of the voltage indicates 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 30, 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 (manufactured by Nippon Vacuum Optical Co., Ltd.) having the characteristics shown in FIG. 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 results of the comparative sensor are shown in FIG. In FIG. 11, line (m) is a reference line showing 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 (n) line is a measured line of an optical sensor having no photo-induced current amplification effect, and FIG. 12 shows changes in quantum efficiency during light irradiation.

On the other hand, in the photosensor according to the present invention, as shown in FIG. 13 as an example, the photoinduced current increases during 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 the integrated information-recording medium is formed in a matrix on a card substrate and packaged, and a photosensor having a photo-induced current amplification effect is used, and high sensitivity is achieved. Further, 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 comprises 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, a second electrode layer on a transparent substrate, and an optical layer. An integrated information recording medium in which a photosensor having a conductive 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 is formed in a rectangular shape and formed in a plurality of matrixes on a card substrate. However, it is fixed and stored in a storage case that has a window that can be opened and closed by a shutter.When performing image exposure and reading, the shutter can be opened and closed to perform image exposure and reading on the card substrate through the window. In addition, a plurality of image exposures and readings can be performed one after another by moving and stopping the card substrate. In the packaging-integrated information recording medium of the present invention, a liquid crystal transmittance monitor light reflecting layer is formed in the non-image area of the rectangular information recording medium. Thus, the liquid crystal transmittance can be monitored. In the packaging-integrated information recording medium of the present invention, the photoconductive layer is interposed between the second electrode layer of the photosensor and the non-image area of the rectangular-shaped integrated information recording medium. The current monitoring electrode layer is formed on the opposite side, and the current can be monitored by the current monitoring electrode layer. 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 addition, the packaging-integrated information recording medium of the present invention, on the back side of the substrate on which the rectangular-shaped integrated information recording medium is formed,
An area in which address information can be recorded is formed, and address information can be recorded in that area. 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 an external appearance of a package-integrated information recording medium of the present invention.

FIG. 2 is a diagram showing a configuration of a recording medium stored in a storage case.

FIG. 3 shows an example of a photographing device (camera) using the packaging-integrated information recording medium of the present invention.

FIG. 4 is a diagram showing a configuration of an information recording area.

FIG. 5 is a diagram showing an example of a back surface of a packaging-integrated recording medium of the present invention.

FIG. 6 is a diagram showing an example in which address marks are provided on the back surface of the substrate of the packaging-integrated recording medium of the present invention.

FIG. 7 is a flowchart showing a manufacturing process of a package-integrated information recording medium.

FIG. 8 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. 9 is a diagram showing an example of temperature characteristics of an information recording medium used in the present invention.

FIG. 10 is a diagram showing characteristics of a green filter used in the present invention.

FIG. 11 is a diagram showing measurement results of a conventional sensor that does not have a photoinduced current amplifying action, unlike the photosensor of the present invention.

FIG. 12 is a diagram showing a change in quantum efficiency during light irradiation of an optical sensor having no photoinduced current amplification effect.

FIG. 13 is a diagram showing an increase in photoinduced current at the time of light irradiation in the photosensor having a photoinduced current amplification effect according to the present invention.

FIG. 14 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]

 1 Storage Case 2 Connector 3 Shatter 4 Handle 5 PCB 6 Substrate 7 Information Recording Area 8 Image Forming Area 9 Lens 10 Prism 11 Housing 12 Connector Receiver 13 Flexible Multicore Cable 14 Second Electrode Layer 15 First Electrode Layer 16 Current Monitor electrode layer 17 Address recording electrode layer 18 Photographic information recording electrode layer 19 Light reflecting layer 20 First electrode terminal 21 Photoconductive layer 22 Liquid crystal recording layer 23 Second electrode terminal 24 Current monitor electrode terminal 25 Magnetic stripe 26 IC Module 27 Address Mark 28 Position Mark 29 Address 30 Optical Sensor 31 Information Recording Medium 32 Dielectric Layer 33 Charge Generation Layer 34 Charge Transport Layer 35 Power Supply 36 Switch 37 Resistance 38 Overcoat Layer 39 Current Monitor Electrode

 ─────────────────────────────────────────────────── ─── 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 (7)

[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. A window that is opened and closed by a shutter is formed by forming an integral 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 to form a rectangular shape into a plurality of matrixes on a card substrate. A packaging-integrated information recording medium, which is fixedly stored in a storage case having a portion. 2. The packaging-integrated information according to claim 1, wherein a light-reflecting layer for liquid crystal transmittance monitor is formed in a non-image area of the rectangular-shaped integral-type information recording medium. recoding media. 3. A current monitoring electrode on the opposite side of the second electrode layer of the photosensor via the photoconductive layer in the non-image area of the rectangular information recording medium. The packaging-integrated information recording medium according to claim 1, wherein a layer is formed. 4. 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. . 5. 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-shaped integrated information recording medium is formed. Integrated information recording medium. 6. The 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. . 7. An overcoat layer is provided between the first electrode layer and the liquid crystal recording layer.
The packaging-integrated information recording medium described.