JPH0850299A - Electrode contact structure of integral type information recording medium - Google Patents

Abstract

PURPOSE:To prevent conduction and generation of electric discharge in the electrode contact parts of an integral type information recording medium and to make it possible to deal with formation of products such as cameras by providing the above recording medium with contacts of respective electrodes in the non-electrode parts of the other-side electrodes or positions facing these non-electrode parts. CONSTITUTION:The electrodes formed on the upper side of an information recording layer 31 are formed in a pattern form and the electrodes formed on the lower side of the information recording layer 31 are formed as common electrodes. The upper patterned electrodes 33 are formed from the left end toward the right end exclusive of the width (non-electrode parts) from the edge at the right end. On the other hand, the lower canon electrodes 32 are formed over the entire surface exclusive of the prescribed spacings (non-electrode parts) from the edge on the left end side of the medium, and are further formed to be turned to the rear side through the side face of the substrate 30. The contacts C1 are formed in the positions facing the non-electrode parts of the lower common electrodes 32 at the left side end of the upper patterned electrodes 33. On the other hand, the contacts C2 on the lower common electrode 32 side are formed in the positions facing the non-electrode parts of the upper patterned electrodes 33 on the rear side of the substrate 30.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode contact structure of an integrated type 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.

[0002]

2. Description of the Related Art Conventionally, a polymer-dispersed liquid crystal recording medium having a liquid crystal polymer composite layer in which a resin phase and a liquid crystal phase are separated from each other and formed on an electrode, and a photoconductive layer on the electrode layer There is known an integrated information recording medium in which the formed optical sensor is laminated and an image is recorded by voltage application exposure. FIG. 1 shows such an integrated information recording medium. In the figure, 10 is an optical sensor and 20 is a liquid crystal recording medium.
In the optical sensor 10, a transparent electrode 12 and a photoconductive layer 13 are sequentially laminated on a transparent support 11, and a liquid crystal recording medium 20 has a liquid crystal layer having a resin phase and a liquid crystal phase separated on a transparent electrode 22. The molecular complex layer 23 is laminated. The photoconductive layer 13 has a single layer structure such as amorphous selenium or amorphous silicon as an inorganic photoconductive layer, polyvinylcarbazole to which trinitrofluorenone is added as an organic photoconductive layer, or polyvinyl butyral as an azo pigment as a charge generation layer. It is possible to use, for example, a layer in which a charge dispersion layer is dispersed in a resin such as the above and a layer in which a hydrazone derivative is mixed with a resin such as a polycarbonate as a charge transfer layer are laminated. In the integrated information recording medium, as shown in FIG. 1A, a liquid crystal recording medium is directly laminated on an optical sensor, and as shown in FIG. 1B, a transparent dielectric intermediate layer 24 is interposed. There are a transmissive type and a reflective type in which the intermediate layer is a dielectric mirror.

As shown in FIG. 2, when a voltage is applied between the electrodes 12 and 22 of such an integral type information recording medium by a power source 30 and visible light is irradiated as writing light, the photoconductive layer is generated according to the exposure intensity. The conductivity of 13 changes, the electric field applied to the liquid crystal polymer composite layer 23 changes, and the alignment state of the liquid crystal changes, which state is maintained even after the applied voltage is turned off and the electric field is removed. Will be recorded.

[0004]

By the way, 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. When such a recording medium is stored in a camera, for example, and an image is taken, if the electrode contact is pressed with a predetermined pressure to apply a voltage, conduction occurs between the recording medium and the counter electrode, or a discharge occurs. Occurs and damages the recording medium.

The present invention has been made in view of the above points, and prevents the occurrence of electrical continuity or discharge at the electrode contact portions of the integrated information recording medium, thereby enabling the commercialization of a camera or the like. An object is to provide an electrode contact structure of a recording medium.

[0006]

The present invention is directed to a liquid crystal recording medium in which a liquid crystal polymer composite layer in which a resin phase and a liquid crystal phase are present in a phase separated state is laminated on an electrode layer, and an electrode on a transparent substrate. Layer, a photosensor having a photoconductive layer formed thereon is laminated directly or with an intermediate layer interposed so that the liquid crystal polymer composite layer and the photoconductive layer face each other. The patterned electrode and the other electrode are used as a common electrode, and the patterned electrode and the common electrode have a non-electrode portion at one end on the left and right opposite sides of the integrated information recording medium. It is characterized in that it is provided at a non-electrode portion of the electrode or at a position facing the non-electrode portion. Further, the present invention is a liquid crystal recording medium comprising a liquid crystal polymer composite layer, which is present in a state where a resin phase and a liquid crystal phase are phase-separated, laminated on an electrode layer,
In an integrated information recording medium, an electrode layer on a transparent substrate, and an optical sensor having a photoconductive layer formed thereon are laminated directly or with an intermediate layer interposed so that the liquid crystal polymer composite layer and the photoconductive layer face each other. Both of the electrodes are patterned electrodes, and one end of each of the patterned electrodes on the opposite side of the integrated information recording medium is a non-electrode part, and the contact of each electrode is the non-electrode part of the other electrode. It is characterized in that it is provided at a position facing the electrode part or the non-electrode part. Further, according to the present invention, a liquid crystal recording medium in which a liquid crystal polymer composite layer in which a resin phase and a liquid crystal phase are present in a phase separated state is laminated on an electrode layer, and an electrode layer and a photoconductive layer are formed on a transparent substrate. In an integrated information recording medium in which an optical sensor and a liquid crystal polymer composite layer and a photoconductive layer are laminated with an intermediate layer interposed, one of the electrodes is patterned and the other is a common electrode. The patterned electrodes and the common electrode have a non-electrode portion at one end on the opposite side of the integrated information recording medium, and a part of the intermediate liquid crystal polymer composite layer side surface is exposed to light. A reflective layer is formed, and a current monitor electrode is formed by drawing the intermediate layer from the end of the liquid crystal polymer composite layer side surface of the intermediate layer to the upper surface or the back surface of the recording medium so as to partially overlap with the electrode layer of the optical sensor.
Each of the contacts of the patterned electrode, the common electrode, and the current monitoring electrode is provided at the non-electrode portion or at a position facing the non-electrode portion. Further, the present invention is a liquid crystal recording medium in which a liquid crystal polymer composite layer existing in a state where a resin phase and a liquid crystal phase are phase-separated, and an electrode layer on a transparent substrate,
In an integrated information recording medium in which a photosensor having a photoconductive layer is laminated with an intermediate layer interposed so that the liquid crystal polymer composite layer and the photoconductive layer face each other, both electrodes are patterned electrodes. In each of the patterned electrodes, one end portion on the opposite side of the integrated information recording medium is a non-electrode portion, and light is reflected by a part of the surface of the intermediate layer on the liquid crystal polymer composite layer side. A current monitor electrode is formed by forming a layer and drawing it from the end of the liquid crystal polymer composite layer side surface of the intermediate layer to the upper surface or the back surface of the recording medium so as to partially overlap with the electrode layer of the photosensor. Each of the contact points of the patterned electrode and the current monitoring electrode is provided at the non-electrode portion or at a position facing the non-electrode portion.

[0007]

According to the present invention, one end of the electrode of the liquid crystal recording medium and the end of the electrode of the photosensor on the left and right sides of the recording medium are removed by etching or the like to form a non-electrode portion, and the contact point of each electrode is the contact of the other electrode. It is provided at the non-electrode part or at a position facing the non-electrode part, and a light reflecting layer is further formed on the intermediate layer, and it is drawn from the intermediate layer to the top surface or the back surface of the recording medium so as to partially overlap with the electrode layer of the photosensor, and the current monitor Forming electrodes for
By providing a contact at the non-electrode part or at a position facing the non-electrode part, it is possible to prevent conduction or discharge from occurring in the electrical contact part.

[0008]

EXAMPLE FIG. 3 is a view for explaining an electrode arrangement structure of a recording medium having a liquid crystal polymer composite layer of the present invention, 30 is a substrate,
Reference numeral 31 is an information recording layer, 32 is a lower common electrode, and 33 is an upper pattern electrode. A recording medium having a liquid crystal polymer composite layer in which a resin phase and a liquid crystal phase are present in a phase-separated state has a thickness of about 20 μm as a whole, and is housed in a camera or the like to replace the silver salt film. When it is used as, it is an important issue how to provide the electrode contact. That is, when the electrode is pressed against the electrode contact to apply a voltage to the recording medium, the recording medium is so thin that conduction or discharge may occur.

As shown in the sectional view of FIG. 3A and the top view of FIG. 3B, the information recording layer 3 is used in this embodiment.
The electrode provided on the upper side of 1 is formed in a pattern, the electrode provided on the lower side of the information recording layer 31 is a common electrode, and the upper pattern electrode 33 has a width W (non-electrode portion) from the edge to the right end. Is formed from the left end to the right end, while the lower common electrode 32 is formed on the entire lower surface of the information recording layer 31 on the left end side of the medium, leaving a predetermined interval (non-electrode portion) from the edge. Further, it is formed so as to pass through the side surface of the substrate 30 and turn to the back side. Also, contact point C
1 is a left end side of the upper pattern electrode at a position facing the non-electrode part of the lower common electrode (position marked with “*” in FIG. 3),
The contact C2 on the lower common electrode side is provided on the back side of the substrate 30 at a position facing the non-electrode portion of the upper pattern electrode 33.

As described above, since the mating electrode is not formed on the opposite side of the contact point and the contacts are formed on the opposite side, even if the electrodes are pressed, the contact point C1 of the upper pattern electrode is formed. Conduction does not occur between the contacts C2 of the lower common electrode 32, and there is no problem even when incorporated in a camera or the like.

FIG. 4 is a diagram showing another embodiment of the present invention. The difference from the example of FIG.
The point is that the contact C1 is provided on the back side of the substrate by turning it to the back side of 0. In this example, the contacts C1 and C2 of the upper pattern electrode and the lower common electrode are both the left end and the right end of the back surface of the substrate 30, so that no conduction occurs between the electrode contacts.

In FIGS. 3 and 4, when the electrode is placed below the back side of the substrate, a metal foil is attached or a metal is provided by spot welding, or ion plating, vapor deposition, sputtering, etc. are arbitrarily performed. The electrode may be formed by the above method.

FIG. 5 shows an example in which reinforcing electrodes are further laminated on the contacts C1 and C2.
As shown in (b), for example, the upper electrode or the lower electrode 32 (33) is reinforced by forming an Al electrode, a gold electrode, or the like by coating, vapor deposition, or a combination of coating and annealing. However, I try not to cause contact failure. in this case,
The upper electrode and the lower electrode are made of electrodes such as ITO which are weak in strength, and by providing reinforcing electrodes, they are extremely effective when applied to products such as cameras.

FIG. 6 shows an embodiment of an electrode contact arrangement structure in which the light transmittance of a liquid crystal polymer composite layer or the conductivity of a dark part is measured in order to control the applied voltage or voltage application time to a liquid crystal recording medium. FIG. In the example of FIG. 6, the upper pattern electrode, the lower common electrode, and the electrode contact arrangement are shown in FIG.
This is the same as the one shown in (3) above, and is further provided with a light reflecting layer and a current monitor electrode.

In FIG. 6, a light reflection layer 42 is arranged on the surface of the intermediate layer 24 between the photoconductive layer 13 and the liquid crystal polymer composite layer 23, and light is emitted from the light emitting diode 40 to reflect the reflected light. The light is received by the light receiving element 41 such as, and the alignment state of the liquid crystal polymer composite layer 23 is detected. On the other hand, the current monitoring electrode 43 is formed below the surface of the intermediate layer 24 so as to partially overlap the upper electrode 33, and is formed below the back surface of the substrate 30 to form the lower common electrode 32 and the current monitoring electrode. 43
The electrical conductivity of the optical sensor is measured by measuring the current flowing between the sensor and the sensor. By measuring the light transmittance of the liquid crystal polymer composite layer or the conductivity of the photosensor, the photographing condition can be set to the optimum state. Note that FIG.
, The contact C1 of the upper electrode is provided in a portion where the lower electrode is etched and does not intersect with the current monitoring electrode 43, and the contact C2 of the lower common electrode is the back surface of the substrate, and the contact of the current monitoring electrode 43. C3 is the back surface of the substrate and is on the opposite side of the contact C2. Further, as the patterning method of the upper electrode, mask dry patterning is desirable, and the lower electrode may be formed by resist patterning, mask dry pattern, resist dry etching or the like.

Next, a combination of electrode arrangements when the lower electrode is a common electrode and the upper electrode is a pattern will be described with reference to FIGS. In addition, FIG.
(D) and FIGS. 8 (a) to 8 (d), (a-1) in FIG.
-(D-1) is a top view, (a-2)-(d-2) is a side view.

In the example shown in FIG. 7A, the contacts C1 and C2 of the upper electrode and the lower common electrode are both provided on the upper surface side of the recording layer, and the lower common electrode 32 is etched at the contact C1 of the upper electrode. The contact C2 of the partial and lower common electrode 32 is located at a position avoiding the upper electrode by moving a part of the electrode to the upper surface of the recording layer. Therefore, in the example of FIG. 7A, the upper surface of both the upper electrode and the lower common electrode serves as an electrical contact portion.

In the example of FIG. 7B, the contact C2 of the lower common electrode 32 is provided at a position where a part of the electrode is lowered to the back side of the substrate to avoid the upper electrode, and the contact C1 of the upper electrode is the recording layer. The upper surface of the electrode is located so as to avoid the lower electrode, and the electric contact portions of the respective electrodes are surfaces on the opposite sides.

In FIG. 7 (c), the upper electrode 33 is turned downward and the right end on the back side of the substrate is used as a contact point C1, and the contact C2 of the lower common electrode 32 is turned over a part of the electrode so that the upper electrode is turned above the medium. As the right end that is avoided, the upper side of the medium and the back side of the substrate serve as electrical contact portions.

In FIG. 7 (d), both the upper electrode and the lower common electrode are lowered to the back side of the substrate, and the positions where the electrodes do not overlap each other are defined as contacts C1 and C2.

FIG. 8A shows an example in which electrode contacts are provided on the opposite sides of the upper surface of the medium to the left and right sides of both the upper electrode and the lower electrode.
Contact points C1 and C2 are the non-electrode portions of the counter electrodes or the positions facing the non-electrode portions.

8 (b), (c) and (d) are shown in FIG.
It is the same as (b), (c) and (d) except that the positions of the contacts C1 and C2 are on the left and right sides.

In this way, the contact point C between the upper electrode and the lower electrode
Considering the upper and lower sides of the medium and the right and left sides of the medium, eight examples of the arrangement examples of C1 and C2 are possible, and it is possible to devise so that conduction does not occur through the mutual contact points. In addition to such combinations of contact positions of the upper and lower electrodes,
Further, it is possible to combine the current monitor electrodes described above with reference to FIG. 6 above and below the medium and to the left and right of the medium, and it is possible to provide respective contacts based on these combinations.

9 and 10 are views showing an embodiment in which the lower electrode is a patterned electrode and the upper electrode is a common electrode.
In the example of FIG. 9, the lower electrode 32 is lowered to the back side of the substrate 30, and the upper common electrode 33 and the lower electrode 32 are respectively etched to form contacts C1 and C2 at the end positions where the opposite electrode does not exist. . Also in this embodiment,
As described with reference to FIGS. 3 to 8, it is possible to consider the upper and lower sides of the medium and the right and left sides of the medium so that the contact points of the two are not short-circuited.

FIG. 10 further shows a reflective layer for measuring liquid crystal transmittance,
It shows an example of providing a dark current measurement electrode of the optical sensor,
Similar to the example shown in FIG. 6, except that the upper electrode is a common electrode and the lower electrode is a patterned electrode. In this case as well, the current monitor for the combination of the contact positions of the upper electrode and the lower electrode is further illustrated. A combination in which electrodes are provided above and below the medium and on the left and right of the medium is also possible.

FIG. 11 shows an example in which both the upper electrode and the lower electrode are patterned. In addition, FIG. 11 (a), (b)
In the figure, (a-1) and (b-1) are side views and (a-2) and (b-2) are top views. FIG. 11 (a)
In FIG. 11, the contacts C1 and C2 are taken out from the back side of the substrate by lowering both the upper electrode and the lower electrode.
In the example of (b), only the lower electrode is turned downward, the upper electrode has a contact point C1 on the upper surface, and the lower electrode has a contact point C2 on the back side of the substrate.
Is provided.

FIG. 12 shows an example in which a light reflecting layer 42 and a current monitoring electrode 43 are further provided when both the upper electrode and the lower electrode are patterned. 12 (a) is a front view, FIG. 12 (b) is a top view, and FIG. 12 (c) is a side view. In the present embodiment, the upper electrode, the lower electrode, and the current monitoring electrode are both lowered, Contact C on the back side of the board
1, C2, C3 are provided, and the current monitoring electrode 43 is shown in FIG.
As shown in (b), it is provided in the non-image portion A so that the dark current can be measured.

FIG. 13 shows another embodiment in which both the upper electrode and the lower electrode are patterned, and a light reflecting layer and a current monitor electrode are provided. In this embodiment, the contact C1 of the upper electrode is on the upper surface. Further, the contact C2 of the lower electrode is provided on the back surface of the substrate while being lowered, and the contact C3 of the electrode for current monitoring is provided on the back surface of the substrate.

[Structure and Material Description of Optical Sensor] The photoconductive layer of the optical sensor of the present invention may be composed of a single layer or a laminated body. Here, the laminated optical sensor will be described. To do. FIG. 14 is a cross-sectional view for explaining the laminated photosensor, in which 11 is a substrate, 12 is an electrode, 13 is a photoconductive layer, 13 'is a charge generation layer, and 13' is a charge transport layer. As shown in the figure, the stacked photosensor is formed by sequentially stacking a charge generation layer and a charge transport layer on an electrode, and the charge generation layer 13 'includes a charge generation substance and a binder. Is 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. 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 0.1 to 10 parts by weight, preferably 0.2 to 10 parts by weight of the binder with respect to 1 part by weight of the charge generating agent.
It is desirable to use 1 part by weight. The thickness of the charge generation layer after drying is 0.01 to 1 μm, preferably 0.1 to 0.5 μm, 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 also be formed alone without using a binder.

The charge-transporting layer 13 "comprises a charge-transporting substance and a binder. The charge-transporting substance is a substance having a good property of transporting charges generated in the charge-generating layer, and is, for example, an oxazole-based, thiazole-based or triazole-based. There are phenylmethane type, styryl type, stilbene type, hydrazone type, carbazole type, enamine type, aromatic amine type, triphenylamine type, butadiene type, polycyclic aromatic compound type, etc., and make them substances with good hole transport properties. As the binder, the same binders as those in the charge generation layer described above, styrene resin, styrene-butadiene copolymer resin, polyarylate resin, phenoxy resin can be used, but preferably styrene resin, These are styrene-butadiene copolymer resins and polycarbonate resins.
The binder is 0.1 to 1 with respect to 1 part by weight of the charge transport material.
It is desirable to use 0 parts by weight, preferably 0.1 to 1 part by weight. The thickness of the charge transport layer after drying is 1 to
The thickness is 50 μm, preferably 3 to 20 μm. With such a thickness, good sensitivity and image quality can be obtained.

The electrodes 12, it is necessary to have a transparency if opaque later information recording medium, transparent if the information recording medium has a transparency may be either opaque, 10 ⁶ Omega · A material that stably gives a specific resistance of not more than cm, for example, a metal thin film conductive film of gold, platinum, zinc, titanium, copper, iron, tin, tin oxide, indium oxide, zinc oxide,
A metal oxide conductive film such as titanium oxide, tungsten oxide 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 electrode 12 is formed by vapor deposition, sputtering or CV.
It is formed by a method such as D, coating, plating, dipping, or 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.
It has a thickness of about 300 nm and is formed over the entire surface between the information recording layer and an arbitrary pattern. Further, two or more kinds of materials can be laminated and used.

The substrate 11 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. 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.

If the electrode 12 is transparent, a layer having an antireflection effect may be laminated on the other surface of the substrate on which the electrode 12 is provided, or the antireflection effect may be exhibited. The antireflection property may be imparted by adjusting the thickness of the transparent substrate or by combining the two.

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 it is less than 0.001 part by weight, it does not show any action,
If the amount is more than 0 parts by weight, the image quality is adversely affected.

A photo-induced current amplification layer may be provided between the photosensor electrode and the photoconductive layer.

The photo-induced current amplification layer is provided between the electrode 12 and the photoconductive layer 13 or the charge generation layer 13 '. The detailed reason for this is unknown, but the current generated by photo induction in the photosensor is The function of amplifying, controlling the charge carrier injecting property from the electrode 12 to the photoconductive layer 13 or the charge generating layer 13 'to control the voltage substantially applied to the information recording medium, and the function of amplifying the light from the electrode 12 Conductive layer 13
Alternatively, it has a function of making charge carrier injecting property into the charge generation layer 13 'uniform and reducing noise and unevenness of information recorded on the information recording medium.

For the photoinduced current amplification layer, the same binders as those used in the charge generation layer described above can be used, and further, soluble polyamide, phenol resin, polyurethane, potiurea, casein, polypeptide, polyvinyl alcohol, polyvinylpyrrolidone. , A maleic anhydride polymer, a quaternary ammonium salt-containing polymer, a cellulose compound and the like can be used, and the binder resins can be used alone or in combination of two or more. Particularly, vinyl formal resin, vinyl acetal resin, and vinyl butyral resin are preferable. The thickness of the photoinduced current amplification layer is preferably 0.01 to 10 μm, preferably 0.3 to 3 μm, and it can be applied by a method such as dip coating, roll coating, spin coating or the like. If it is thinner than 0.01 μm, the effect of reducing image noise is lost, and if it is thicker than 10 μm, injection of charge carriers from the electrode to the charge generation layer is hindered.

If necessary, the photoinduced current amplification layer may include various electron-accepting substances, photoconductive substances, inorganic salts,
Organic salts are added, and the additives can be used alone or in combination of two or more.

These additives are added in a proportion of 0.1 to 1000 parts by mol, preferably 1 to 100 parts by mol, relative to 100 parts by mol of the binder resin. They can be used in combination, and in particular, it is preferable to use a combination of an electron-accepting compound and an organic photoconductive pigment such as a combination of a substituted benzoquinone and an azo pigment because a large amplifying effect can be obtained.

[Production of Laminated Photosensor] An ITO film having a sheet resistance of 80 Ω / port 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. The electrode is cleaned with a scrubber cleaning machine (trade name: Plate Cleaner Model 602 Ultratech Co., Ltd.) for 2 seconds of pure water injection, 20 seconds of scrubber cleaning, 15 seconds of pure water rinse, 25 seconds of water removal by high speed rotation, 55 seconds of infrared drying. The washing process was performed twice. A charge generating substance is placed on the electrode and the following structure

[0042]

Embedded image

3 parts by weight of a bisazo pigment having a vinyl chloride-vinyl acetate mixed resin (Denka Vinyl # 1000D manufactured by Denki Kagaku Kogyo and 18,32 manufactured by Aldrich).
5.89J 75:25 mixture with vinyl acetate resin)
1 part by weight was mixed with 98 parts by weight of 1,4-dioxane and 98 parts by weight of cyclohexanone, and sufficiently kneaded with a mixer to obtain a coating solution, which was spun at 1400 rpm,
After coating for 0.4 seconds, after coating, a film is formed on the surface of the coating film, and the coating film surface is left without dust until leveling and drying, and then 1
After drying at 00 ° C. for 1 hour, a charge generation layer having a film thickness of 300 nm was laminated.

On the charge generating layer, the following structure was formed as a charge transporting substance.

[0045]

Embedded image

A butadiene derivative having
-405) 50 parts by weight and 10 parts by weight of styrene-butadiene copolymer resin (Clearene 730L manufactured by Denki Kagaku Kogyo Co., Ltd.) were added to 68 parts by weight of chlorobenzene and 68 parts of dichloromethane.
Parts by weight and 136 parts by weight of 1,1,2-trichloroethane are uniformly dissolved to obtain a coating solution, which is 350 rpm with a spinner.
After coating for 0.4 m, the film is formed on the surface of the film, and the film is left in the windless state until leveling does not occur. After leveling and drying, 80 ° C for 2 hours. An optical sensor according to the present invention having a photoconductive layer having a film thickness of 20 μm, which comprises a charge generation layer and a charge transport layer, is prepared by drying and stacking the charge transport layer, and the photosensor is manufactured at room temperature and a relative humidity of 60% or less in a dark place. It was aged for 3 days.

[Structure and Material of Information Recording Medium] The information recording medium 20 will be described. First, as an information recording medium in the present invention, a case where the information recording layer is a polymer dispersed liquid crystal is mentioned.

The polymer-dispersed liquid crystal has a structure in which resin particles are dispersed in the liquid crystal phase, and the liquid crystal material may be a smectic liquid crystal, a nematic liquid crystal, a cholesteric liquid crystal, or a mixture thereof. As a liquid crystal, it retains its orientation and holds information permanently,
From the viewpoint of so-called memory property, it is preferable to use a smectic liquid crystal.

Examples of the smectic liquid crystal include a liquid crystal substance exhibiting a smectic A phase such as a cyanobiphenyl type, a sinoterphenyl type, a phenyl ester type having a long carbon group as a terminal group of a substance exhibiting liquid crystallinity, and a ferroelectric substance having a ferroelectric property. A liquid crystal material exhibiting a smectic C phase used as a liquid crystal,
Alternatively, a liquid crystal substance exhibiting smectic H, G, E, F or the like can be given.

The material for forming the resin particles is, for example, an ultraviolet curable resin which is compatible with the liquid crystal material in the state of monomer or oligomer, or a solvent common to the liquid crystal material in the state of monomer oligomer. Those having compatibility 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,
For example, an acrylic resin, a methacrylic resin, a polyester resin, a polystyrene resin, a copolymer containing these as a main component, an epoxy resin, a silicone resin, or the like may be used.

The ratio of the liquid crystal material to the resin used is such that the liquid crystal content is 10% by weight to 90% by weight, preferably 40% by weight.
It is preferable to use it in an amount of 80% by weight, and if it is less than 10% by weight, the light transmittance is low even if the liquid crystal phase is aligned due to information recording, and if it exceeds 90% by weight, a phenomenon such as liquid crystal bleeding occurs. However, image unevenness is not preferable.

Since the film thickness of the information recording layer affects the resolution, the film thickness after drying is 0.1 μm to 10 μm, preferably 3 μm.
It is preferable that the thickness is in the range of 8 μm to 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.

[Fabrication of Information Recording Medium] ITO having a thickness of 100 nm was formed as a conductive layer on a glass substrate having a thickness of 1.1 mm.
After the film was formed by sputtering and the electrode was obtained, the surface was washed.

On this electrode, a polyfunctional monomer (dipentaerythritol hexaacrylate, manufactured by Toagosei Kagaku,
M-400) 40 parts by weight, photo-curing initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one,-
Ciba Geigy, Darocure 1173) 2 parts by weight, liquid crystal 50 parts by weight (90% of smectic liquid crystal (Merck S-6), nematic liquid crystal (Merck),
10% of E31LV), 3 parts by weight of a surfactant (Sumitomo 3M, Florard FC-430) in xylene 9
The coating solution obtained by uniformly dissolving in 6 parts by weight was coated using a blade coater having a gap of 50 μm, dried at 47 ° C. for 3 minutes, and then dried at 47 ° C. for 2 minutes under reduced pressure. Immediately, the coating film was cured by irradiation with 0.3 J / cm ² of ultraviolet rays to obtain an information recording medium having an information recording layer having a film thickness of 6 μm.

After the liquid crystal was extracted from the information recording layer surface with hot methanol and dried, the internal structure was observed with a scanning electron microscope (S-800 manufactured by Hitachi, Ltd.) at 1000 times. It is covered with a UV-curable resin of 0.6 μm and has a particle size of 0.1 in the liquid crystal phase forming a continuous layer inside the layer.
It had a structure filled with a resin particle phase of μm.

[Structure and Material of Integrated Intermediate Layer] FIG.
Is a cross-sectional view showing an example of the information recording system of the present invention,
In the figure, 21 is a substrate, 22 is an electrode, 23 is an information recording layer, 24
Is a dielectric layer, and the same reference numerals as those in FIG. 2 indicate the same contents.

In this information recording system, the optical sensor and the information recording body are directly laminated, or the optical sensor and the information recording body are separated from each other and opposed to each other. It is directly laminated through. This information recording system is particularly suitable when the photoconductive layer in the optical sensor is formed by coating using a solvent, and when the information recording layer is directly formed by coating on the photoconductive layer, the information recording is caused by their interaction. Which can prevent image unevenness due to liquid crystal elution in the above or the photoconductive material being eluted due to the solvent for forming the information recording layer, and also enables integration of the optical sensor and the information recording medium. Is.

In forming the dielectric layer 24, it is necessary that the dielectric layer 24 is insoluble in both the photoconductive layer forming material and the information recording layer forming material, and also has conductivity. It is necessary not to. 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, and it is preferable that the film thickness be 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 to 3 μm is preferable. 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, inorganic materials such as SiO ₂ , TiO ₂ , CeO ₂ , Al ₂ O ₃ and Ge are used.
_{O 2, Si 3 N 4,} AiN, TiN, MgF 2, ZnS, a combination of a titanium dioxide silicon dioxide, a combination of zinc sulfide and magnesium fluoride, using a combination of aluminum oxide and germanium, evaporation, sputtering , Chemical vapor deposition (C
It may be formed by stacking by the VD) method or the like. 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-4-24722,
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. However, by selecting the combination of the liquid crystal and the resin, the information is oriented once and the visualized information is erased. Instead, a memory property can be provided. 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.

[Photo-induced Current Amplification Function of Optical Sensor] In the optical sensor of the present invention, the electric field or the amount of electric charge applied to the information recording medium at the time of irradiating light to the optical sensor is amplified with the irradiation of light and If the voltage is continuously applied even after the irradiation is finished, the increased conductivity is sustained by relaxation decay,
It has the function of continuously applying the electric field or the amount of charge to the information recording medium.

The photo-induced current amplifying action in the optical sensor of the present invention will be described in detail. In an optical sensor in which an ITO electrode is provided on transparent glass and a photoconductive layer is laminated on the electrode as an optical sensor for measuring amplification effect, a gold electrode of 0.16 cm ² is laminated on the photoconductive layer. And
A constant DC voltage is applied between the two electrodes with the ITO electrode as a positive electrode, and light is irradiated for 0.033 seconds on the substrate side 0.5 seconds after the start of voltage application, and the behavior of the current value in the photosensor during the measurement time is measured. The measurement is performed from the start of light irradiation (t = 0). The irradiation light is a xenon lamp (L2274 manufactured by Hamamatsu Photonics) as a light source, and green light (manufactured by Nippon Vacuum Optical Co., Ltd.) is used to select and irradiate the edge light, and the irradiation light intensity is measured by an illuminance meter (manufactured by Minolta) Measured at 20 lux. FIG. 16 shows the filter characteristic.

When irradiated with light at this light intensity, a transparent substrate,
Considering the light transmittance of the ITO film and the spectral characteristics of the filter, 4.2 × 10 ¹¹ photons / cm ² seconds are incident on the photoconductive layer. When all the incident photons are converted into photocarriers, theoretically, a current of 1.35 × 10 ⁻⁶ A / cm ² is generated as a photocurrent per unit area.

Here, in the case of measuring with the measuring device, the ratio of the photo-induced current actually generated by the photosensor to the theoretical photocurrent (the photo-induced current value actually generated by the photosensor / 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 flowing in the part not irradiated with light, and is caused by light irradiation above the base current during or after light irradiation. It means that a current flows, which 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 result of the measuring device. . First, the measurement result of the comparative sensor is shown in FIG. In FIG. 17, the (m) line is a reference line showing the theoretical value (1.35 × 10 ⁶ A / cm ² ), and the state where the light irradiation was performed for 0.033 seconds and the voltage application was continued after the light irradiation. Indicates. Line (n) is a measured line of an optical sensor that does not have a photoinduced current amplification effect, and the increase in photocurrent during light irradiation is small, and its value is also a theoretical value (1.35 × 10 ⁶ A /
cm ² ) and the quantum efficiency in this comparative sensor is constant at approximately 0.4. The change in quantum efficiency during light irradiation in this comparative sensor is as shown in FIG.

On the other hand, in the photosensor of the present invention, as an example, as shown in FIG. 19 (n), the photoelectromotive force increases during light irradiation. The line (m) is the theoretical value (1.35).
× 10 ⁶ A / cm ² ). The quantum efficiency of this optical sensor is as shown in FIG. 20, and as is clear from this, it can be seen that the quantum efficiency exceeds 1 in about 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 continues to flow by continuing the voltage application even after the light irradiation, and the photoinduced current can be subsequently taken out to continuously obtain the optical information. You can

[Semi-Conductivity of Optical Sensor] The optical sensor of the present invention is semi-conductive as a whole, and the specific resistance in the dark is 10 ⁹ to 10 ¹³ Ω · cm from the flowing current density. Is preferred. Particularly, the specific resistance is 10 ¹⁰ to 10 ¹¹ Ω · cm
The amplification effect is remarkable in the range of. Resistivity is 10 ¹³
For optical sensors larger than Ω · cm, 10 ⁵ to 10 ⁶ V /
In the electric field strength range of cm, it does not exhibit the amplifying action as in the optical sensor of the present invention. Further, in an optical sensor having a specific resistance of less than 10 ⁹ Ω · cm, a large amount of current flows, and noise due to the current is likely to occur, which is not preferable.

On the other hand, the photosensitive element used for general electrophotography has a dark resistivity of 10 ¹⁴ to 10 ¹⁶ Ω · c.
m is used, the sensor of the present invention cannot achieve its purpose in electrophotography, and a photosensor having a photoconductive layer having a large dark resistivity for electrophotography is generally used. It cannot be used for the purposes of the invention.

When the information recording layer of the information recording medium is a polymer dispersed liquid crystal, it is necessary to set the sensitivity of the optical sensor in the operating voltage range of the liquid crystal.

That is, the contrast voltage, which is the difference between the potential (light potential) applied to the information recording medium in the exposed area and the potential (dark potential) applied to the information recording medium in the unexposed area, is the contrast voltage in the information recording medium. It is necessary to have a certain size in the operating voltage region of the liquid crystal.

Therefore, for example, the dark potential applied to the liquid crystal layer in the unexposed portion of the photosensor needs to be set to about the operation start potential of the liquid crystal. Therefore, when the resistivity of the information recording medium is 10 ¹⁰ to 10 ¹³ Ω · cm at room temperature and the electric field of 10 ⁵ to 10 ⁶ V / cm is applied to the optical sensor,
The conductivity is required to the extent that a base current of 0 ⁻⁴ to 10 ⁻⁷ A / cm ² is generated, and the range of 10 ⁻⁵ to 10 ⁻⁶ Acm ² is preferable.

[0073] In the optical sensor of the base current is less than 10 ^-7 A / cm ² without alignment in the liquid crystal layer is exposed state and ^10-4
In an optical sensor with a base current of A / cm ² or more, a large amount of current flows at the same time as voltage application even in the unexposed state, and the liquid crystal is aligned, and even if exposed, no difference in transmittance can be obtained between the exposed portion and the unexposed portion. . In addition, since there are some liquid crystals having different operating voltages and ranges, it is necessary to consider the voltage distribution in the information recording medium when setting the applied voltage and the voltage application time.

[0074]

As described above, according to the present invention, an electrode contact of an extremely thin recording medium, which is an information recording medium in which an optical sensor and a liquid crystal recording medium are integrated, is pressed by a metal contact or the like to apply a voltage. Since it is possible to prevent conduction between electrodes and the occurrence of discharge, it is possible to properly apply a voltage and perform good image exposure even when incorporated in a camera or the like.

[Brief description of drawings]

FIG. 1 is a diagram illustrating an optical sensor and a liquid crystal recording medium.

FIG. 2 is a diagram illustrating an integrated liquid crystal recording medium.

FIG. 3 is a diagram illustrating an electrode arrangement structure of the recording medium of the present invention.

FIG. 4 is a diagram showing another embodiment of the present invention.

FIG. 5 is a diagram showing an example in which a reinforcing electrode is laminated on a contact portion.

FIG. 6 is a diagram showing another embodiment of the electrode arrangement structure.

FIG. 7 is a diagram illustrating a combination of electrode arrangements when the lower electrode is a common electrode and the upper electrode is a pattern shape.

FIG. 8 is a diagram illustrating a combination of electrode arrangements when the lower electrode is a common electrode and the upper electrode is a pattern shape.

FIG. 9 is a diagram showing an example in which a lower electrode is patterned and an upper electrode is a common electrode.

FIG. 10 is a diagram showing an example in which a light reflecting layer and a dark current measuring electrode are provided.

FIG. 11 is a diagram showing an example in which both the upper electrode and the lower electrode are patterned.

FIG. 12 is a pattern of both the upper electrode and the lower electrode,
It is a figure which shows the example which provided the light reflection layer and the electrode for a current monitor further.

FIG. 13 is a pattern of both the upper electrode and the lower electrode,
It is a figure which shows another Example which provided the light reflection layer and the electrode for a current monitor further.

FIG. 14 is a diagram illustrating a stacked optical sensor.

FIG. 15 is a diagram showing an example in which an optical sensor and an information recording body are directly laminated via a dielectric layer.

FIG. 16 is a diagram showing a filter characteristic.

FIG. 17 is a diagram showing a measurement result of a comparative sensor.

FIG. 18 is a diagram showing quantum efficiency characteristics.

FIG. 19 is a diagram showing a current change of an optical sensor according to the present invention.

20 is a diagram showing quantum efficiency characteristics of the optical sensor of FIG.

[Explanation of symbols]

10 ... Optical sensor, 20 ... Liquid crystal recording medium, 24 ... Intermediate layer,
30 ... Substrate, 31 ... Information recording layer, 32 ... Lower electrode, 33
... upper electrode, 40 ... light emitting element, 41 ... light receiving element, 42 ...
Light-reflecting layer, 43 ... Electrodes for current monitoring.

Claims (6)

[Claims] 1. A liquid crystal recording medium in which a liquid crystal polymer composite layer in which a resin phase and a liquid crystal phase are present in a phase separated state is laminated on an electrode layer, and an electrode layer and a photoconductive layer are formed on a transparent substrate. In an integrated type information recording medium in which a liquid crystal polymer composite layer and a photoconductive layer are laminated directly or with an intermediate layer interposed, one of the electrodes is a patterned electrode and the other is a common electrode. Each of the patterned electrodes and the common electrode has a non-electrode portion at one end on the left-right opposite side of the integrated information recording medium, and the contact of each electrode is the non-electrode portion or the non-electrode of the counterpart electrode. An electrode contact structure for an integrated information recording medium, characterized in that the electrode contact structure is provided at a position facing the section. 2. The electrode contact structure according to claim 1,
An electrode of an integrated information recording medium, characterized in that each patterned electrode and / or common electrode is formed by drawing it to the upper surface or the back surface of the recording medium, and a contact is formed on the electrode part of the drawn upper surface or the back surface. Contact structure. 3. A liquid crystal recording medium in which a liquid crystal polymer composite layer in which a resin phase and a liquid crystal phase are present in a phase separated state is laminated on an electrode layer, and an electrode layer and a photoconductive layer are formed on a transparent substrate. In an integrated information recording medium in which an optical sensor and a liquid crystal polymer composite layer and a photoconductive layer are laminated so as to face each other directly or with an intermediate layer interposed, both electrodes are patterned electrodes, and each patterned The electrode has a non-electrode portion at one end on the left-right opposite side of the integrated information recording medium,
An electrode contact structure for an integrated information recording medium, characterized in that the contact of each electrode is provided at the non-electrode part of the counter electrode or at a position facing the non-electrode part. 4. The electrode contact structure according to claim 3,
At least one of both patterned electrodes is formed by being drawn to the upper surface or the back surface of the integrated information recording medium, and a contact is formed at the electrode portion of the drawn upper surface or the back surface. Electrode contact structure of medium. 5. A liquid crystal recording medium in which a liquid crystal polymer composite layer in which a resin phase and a liquid crystal phase are present in a phase separated state is laminated on an electrode layer, and an electrode layer and a photoconductive layer are formed on a transparent substrate. In an integrated information recording medium in which an optical sensor and a liquid crystal polymer composite layer and a photoconductive layer are laminated with an intermediate layer interposed, one of the electrodes is patterned and the other is a common electrode. The patterned electrodes and the common electrode have a non-electrode portion at one end on the opposite side of the integrated information recording medium, and a part of the intermediate liquid crystal polymer composite layer side surface is exposed to light. A reflective layer is formed, and a current monitor electrode is formed by drawing the intermediate layer from the end of the liquid crystal polymer composite layer side surface of the intermediate layer to the upper surface or the back surface of the recording medium so as to partially overlap the electrode layer of the optical sensor. Each contact of patterned electrode, common electrode and current monitor electrode An electrode contact structure for an integrated information recording medium, wherein dots are provided at the non-electrode part or at a position facing the non-electrode part. 6. A liquid crystal recording medium in which a liquid crystal polymer composite layer in which a resin phase and a liquid crystal phase are present in a phase separated state is laminated on an electrode layer, and an electrode layer and a photoconductive layer are formed on a transparent substrate. In an integrated information recording medium in which an optical sensor and a liquid crystal polymer composite layer and a photoconductive layer are laminated with an intermediate layer interposed therebetween, both electrodes are patterned electrodes, and each patterned electrode is , The left and right opposite ends of the integral type information recording medium are non-electrode parts, and a light reflecting layer is formed on a part of the surface of the intermediate layer on the liquid crystal polymer composite layer side, An electrode for current monitoring is formed by drawing it from the end of the liquid crystal polymer composite layer side of the intermediate layer to the upper surface or the back surface of the recording medium so as to partially overlap with the electrode layer of the optical sensor,
An electrode contact structure for an integrated information recording medium, wherein each pattern electrode and each contact of the current monitoring electrode are provided at the non-electrode part or at a position facing the non-electrode part.