JPS60192974A - Recording medium - Google Patents

Abstract

PURPOSE:To obtain a recording medium having high sensitivity to an energy signal by providing a photoconductive layer, a monomolecular film or accumulated monomolecular film of a metallic chelate compd. and a transparent base having a transparent electrode on a substrate. CONSTITUTION:When rays 9 having adequate light intensity are irradiated on a recording medium formed by laminating a photoconductive layer 6, a metallic chelate compd. 3, an electrode 7 and a base 8 on a conductive substrate 1, only the photoconductive layer of the irradiated part is made conductive. When an electric field is applied between the substrate 1 and the electrode 7, a strong electric field is impressed between the photoconductive layer which is made conducting and the electrode 7 to have an extreme difference in the intensity of the electric field from the part where the rays are not irradiated. The metallic ions in the monomolecular film or accumulated monomolecular film of the compd. 3 only in the part where the strong electric field is impressed, i.e., the part where the light is irradiated are reduced, by which the metal 10 is freed and the recording image consisting of the metal atoms is formed.

Description

Detailed Description of the Invention [Technical Field] The present invention relates to a novel image recording medium, and more particularly, it relates to a novel image recording medium, and more particularly, to The present invention relates to an image recording medium in which a molecular cumulative film and a transparent support having a transparency 17 (?) are sequentially provided.

[Prior art] Conventionally, energy sources such as light, heat, and electricity have been used.
Various recording media and recording methods are known as recording media and recording methods for recording images by recording images, and some of them have been put into practical use (for example, "Printing L7Ir, IIIJ (Common)"). Among them, there are many research examples regarding recording media and recording methods using metal chelate compounds. Examples of this include Jl, Robillard, Potogra.
fie 5ience and Engine-eri
ng, 8. (19f14) 18. The recording medium disclosed in 2003 forms a visible image by performing imagewise exposure while applying a high electric field, and this recording medium contains compound particles (for example, C
uSCN) is surrounded by a color-forming substance (e.g. Na(Co(
A metal chelate compound such as CsH702)+(NO+)2)+7) is mixed and dispersed in a binder, and this is applied to a conductive substrate to a thickness of several coats. There is. To form an image, a transparent plate made of glass or the like provided with a transparent 5N02 vapor-deposited electrode is placed on the conductor on which the recording medium layer is formed.
It is placed over the conductive substrate 1-, and is exposed to light while applying a high electric field between the 5n07 electrode and the conductive substrate, thereby forming a colored image of metallic cobalt.

Also, JP-A-50-45822 and JP-A-51-1
The recording medium disclosed in No. 30218 is prepared by mixing and dispersing a tellurium metal chelate compound (e.g. dichlorotellurobisacetophenone) and a photosensitizer (e.g. pyrenequinone) in a binder and coating the mixture on a support 1-. It consists of
After imagewise exposure, the recording medium is heated to obtain a colored image of metallic tellurium. Similarly, as a method for obtaining a recorded metal image by exposure and heat treatment, a recording medium made of a β-diketonite metal chelate-1 compound and a photosensitizer is disclosed in JP-A-50-109720 ('). Are known.

Another example is a recording medium using a cobalt complex developed by Kotatsu Co., Ltd. The image formation process in this case is the same as that described above, and a colored clear I image of cobalt is formed by exposure and heat treatment ( As a modification of this, a method has been proposed in which cyan paper is colored using ammonia gas generated from the recording medium during heat development. (m) Complex ((CO(NH3)6)"3CI-)
A photosensitizer (e.g., quinone) and a compound (e.g., 1-(2-pyridylazo)-2-naphthol, hereinafter abbreviated as PAN) that forms a colored chelate with cobalt ions are mixed and dispersed in a binder and supported. It is composed by applying it to the body H. When the recording medium is heated after exposure, cobalt is reduced from trivalent to divalent in the exposed area, and this forms a chelate with PAN. This chelate undergoes a ligand exchange reaction with the hexamine cobalt (■) complex, producing a colored chelate of trivalent cobalt with PAN, and the divalent cobalt ion reacts with completely free PAN to form a chelate. By repeating this process, a colored cobalt trivalent PAN chelate is produced in a chain, and a visible image is formed.

As another example, a metal salt of a higher fatty acid, a metal for the core, and a compound forming a colored chelate are mixed and dispersed in a binder, or two layers containing these compounds separately are formed on a support. It is known that the metal salt and the chelating agent are applied in a molten contact with a chelating agent to form a color by heating according to the recorded image.For example, stearin butyzinc and diphenyl Ml with Kalparan
A red image is obtained by the combination, and a black-purple image is obtained by the combination of ferric stearate and gallic acid.

However, in these conventional technologies, since the recording medium is formed as a film with a thickness of about several micrometers, there are problems such as large image blurring and lack of image clarity. There were some problems. In addition, when forming a film by mixing a compound used as a recording medium with a binder, etc., a step of coating using a solvent is required, and the coloring reaction slows down during the step. The drawback is that it is easy to cause so-called fogging due to the unevenness of the parts. In addition, in order to suppress such undesirable reactions, if each compound is added to a separate layer to create a multilayer structure, the reaction efficiency between each compound will be significantly lowered by 1.'', and the resolution of the image will be lowered. It also had the disadvantage of low sensitivity.Also, when it is necessary to apply an electric field between the recording layers, a high voltage (for example, several hundred ports) must be applied because the recording layer is thick. had to be applied.

OBJECT OF THE INVENTION] An object of the present invention is to provide a recording medium that is highly sensitive to energy signals.

Another object of the present invention is to provide a new recording medium that can provide recorded images with crystal quality and high resolution without fogging or noise.

Still another object of the present invention is to provide a novel recording medium that is reusable.

[Structure of the Invention] That is, the recording medium of the present invention is constituted by sequentially providing a photoconductive layer, a monomolecular film or a medium molecule cumulative film of a metal chelate compound, and a transparent support having a transparent electrode on a support. Ru.

Examples of materials that can be used as the support for the recording medium of the present invention include plates and films made of metals such as glass and aluminum, ceramics, plastics, and the like. When these supports are made of insulating materials, their surfaces must be made conductive by, for example, gold jar Z4 coating or lamination.

In the recording +y body of the present invention, a photoconductive layer is formed on the conductive surface of the 1- support body.

Examples of materials constituting the photoconductive layer include organic photoconductive materials such as polyvinyl chloride/trinitrofluorene; ZnO, Ti07, CdS, and Zn.
Pigment-resin dispersion system photoconductive material in which pigments such as S are dispersed in alkynd resins and polycarbonate resins = l;
Conventionally known materials such as amorphous photoconductive materials such as amorphous silicon can be coated or plasma-enhanced by plasma CVD.
It is formed by means such as. The layer thickness of the optical quadruple layer must be at least equal to or greater than the thickness of the single molecule or cumulative film of the metal layer or compound that is laminated on the J- layer. , and is usually set after IJLIn.

Formed on the surface of a medium-molecular film or a one-molecular-thick molecular-grained film of a metallic conductor compound [-The surface of the conductive layer must be sufficiently clean from an interfacial chemical point of view. .

If the surface of the photoconductive layer is not cleaned in part C, the middle molecule film will be disturbed when the monomolecular layer is transferred from the water surface, and a good middle molecule film or monolayer cumulative film may not be formed, or the film may peel off. It becomes difficult to form an Lrat molecule-film or a middle molecule cumulative film.

The chemical structure of the metal compound capable of forming the middle molecule film or middle molecule accumulation 11 used in the recording medium of the present invention is that it has a hydrophilic part and a hydrophobic part. It is a compound having a structure similar to a so-called surfactant, which is also present in r-. The most typical wood-philic moieties include a carboxyl group and its metal or amine fig, a sulposic acid group and its metal or amine salt, a sulfonamide F group, an amide group, an amino group, an imino group, a hydroxyl group, and a quaternary group. Examples include 7 class amine groups, 7 oxyamino groups, oximino groups, cyazinium groups, guanidine groups, hydrazine groups, phosphoric acid groups, silicic acid groups, and aluminic acid groups. On the other hand, the most typical hydrophobic moiety is a long-chain alkyl group, which is generally a carbon atom f-
The number of carbon atoms is about 5 to 30, more preferably about 10 to 25. Further, as long as the alkyl chain length is appropriate, either a straight chain or a branched chain may be used. Other examples include olefinic hydrocarbon groups such as vinylene, vinylidene, and acetylene, and condensed polycyclic aromatic groups such as phenyl, naphthyl, and anthranyl)1(, m t poly10' such as hypohenyl and terphenyl)'J ' M
There are group groups, etc. These lignophilic portions and hydrophobic portions may each be Chinese-German or a combination of two or more, may be located at both ends of the molecule, or may be located at the center of the molecule. However, metal chelate compounds having arbitrary combinations of lignophilic moieties and hydrophobic moieties within the molecule are not always capable of forming a monomolecule-11'J or intermediate molecule cumulative film. That is, in order to obtain an 11-molecular film or a monomolecular cumulative film by the middle molecule accumulation method, it is necessary to form one molecule on the water surface. When hydrophilicity is strong, the metal chelate compound dissolves in water to form an aqueous solution; on the other hand, when hydrophobicity is superior, the metal chelate compound separates into two phases from water. do. It is possible to form a medium molecular film on the water surface when the molecule's phyllophilicity and hydrophobicity are appropriately balanced. At this time, the metal chelate compound As a whole, the hydrophilic portion is directed toward the aqueous phase, and is adsorbed at the air-water interface to form a monkey molecule n@.

Therefore, it is required that the metal chelate-I compound has a suitable balance between the wood-philic part and the hydrophobic part.

Furthermore, the metal chelate compound that can be used in the recording medium of the present invention is required to be capable of reducing the metal ion in the metal chelate compound and liberating the metal by applying activation energy. be done.

Pd++ and R are alkyl groups having 10 to 3 carbon atoms.

However, in the L formula, H is Ag'', Cu+ or pa
++, R1 is a hydrogen atom, methyl group or ethyl group, R2
represents an alkyl or acyl group having 10 to 30 carbon atoms, and X represents an anion of NO3-1CI-1 or SO2-7.

(C) However, in set 1, X is monovalent, Cu, Co.

Fe, Mn, Ni, Zn, Pb or Pd, R' is a hydrogen atom r.

Methyl group or ethyl group R2 is carbon atom Y-number lθ ~
30 alkyl or alkylcarboxylic acid NoS, x represents an anion such as NO, -1CI-1, SOi'', etc.

In order to produce the recording medium of the present invention by laminating these metal chelate compounds as a monomolecular film or a monomolecular cumulative film on the rough plate 1-, for example, 1. Lang IIlu i
Langmuir-Brosier-Nt J), (developed by R et al.
LB method) is used. The Langmuir-Blodgett method is
In molecules with a structure that has a parent wood group and a hydrophobic group in the molecule,
When the balance between the two (balance of amphiphilic properties) is maintained appropriately, the molecules form a monolayer or a monomolecular layer by turning the parent group downward at the water surface and forming a layer of middle molecules. This is a method for creating a cumulative film of F layers. The monomolecular layer on the water surface 1- has the characteristics of a two-dimensional system. When the molecules are sparsely dispersed, the two-dimensional ideal gas equation, nA=kT, holds between the area per molecule A and the surface pressure (2), resulting in a gas film. Here, k is Boltzmann's constant and T is absolute temperature. If A is made small enough, the intermolecular phase W action will become stronger and the two-dimensional solid will condense 11 degrees (
or solid film). The condensed film can be transferred layer by layer to the surface of a substrate such as a glass. Using this method,
A monomolecular film or a monomolecular layer stack is manufactured, for example, as follows.

First, a metal chelate compound is dissolved in a solvent, and this is expanded into an aqueous phase to precipitate the metal chelate compound in an H shape.

Next, to prevent this precipitate from freely diffusing into the aqueous phase 1- and spreading too much, a partition plate (or a float) is provided to limit the area of development and control the agglomeration of the membrane substance. Obtain the surface pressure [I] which is proportional to the aggregate state. By moving this partition plate, the developed area is reduced to control the state of collection of the film material, and the surface J1:
gradually increase the surface pressure to 1 - 1 to obtain a surface pressure suitable for producing a cumulative film.
can be set. By gently moving the clean substrate vertically while maintaining this surface pressure, the middle molecular film of the metal chelate compound is transferred onto the substrate 1-. A monomolecular film can be produced in this manner, or a monomolecular layer stack 11 can be formed by repeating the above-mentioned operations to form a monomolecular layer stack 11 with a desired degree of accumulation.

In order to transfer the middle molecule film to the substrate l-, in addition to the above-mentioned vertical dipping method, a method such as a horizontal adhesion method or a rotating cylinder D; can be used. The horizontal deposition method is a method in which the substrate is brought into contact with water = li and transferred, and the rotating cylinder method is a method in which a cylindrical nor body is rotated on the water surface to transfer a monomolecular layer onto the substrate surface. In the vertical immersion method described above, when the substrate is lowered in a direction across the water surface, a middle molecular layer is formed on the substrate 1- in which the first layer has parent wood groups facing the substrate side.

When the substrate is heated as described above, one monolayer is added to the other at each step. Since the direction of the film-forming molecules is reversed in the pulling process and the dipping process, according to this method, between each layer, the parent wood group and the parent wood group, and the
A mold film is formed.

On the other hand, the horizontal deposition method is a method in which the substrate is brought into contact with water 47- and transferred, and a monomolecular layer with hydrophobic groups facing the substrate is formed on the substrate. In this case, even if accumulated, there is no change in the direction of the molecules, and an X-shaped film is formed in which the hydrophobic groups face the substrate side in all layers. On the other hand, a cumulative film in which all the layers have parent wood groups facing the substrate side is Z.
It is called a mold membrane.

The rotating cylinder method rotates a cylindrical base on the water surface to generate tg.
This is a method in which a molecular layer is transferred to the surface of a substrate.

The method of transferring the monomolecular layer to the substrate J- is not limited to these methods, and when a large-area substrate is used, a method of extruding the substrate from a substrate roll into an aqueous phase may also be used. Furthermore, the orientation of the aforementioned parent wood group and hydrophobic group toward the substrate is a general rule, and can be changed by surface treatment of the substrate, etc.

The details of these monomolecular film transfer operations are already known and are described, for example, in "New Experimental Chemistry Course 18 Interfaces and Colloids", Volumes 498-507, Maruzen +41.

In this way, when forming a monomolecular cumulative film, after forming the first layer of monomolecular film, dry it in air for 1 minute to remove moisture, solvent, etc. It has been found that by forming a monomolecular film, the accumulation operation can be carried out smoothly without peeling of the accumulated film. In addition, many experiments have shown that the thickness of the monomolecular cumulative film formed in this way is equal to the length of the metal chelate compound molecule multiplied by the number of cumulative times (the number of monomolecular films). Confirmed.

The φ molecule film or monomolecular cumulative film thus formed on the substrate H is strongly fixed between the substrate and the film phase I by i Although this is rare, the adhesion force can also be strengthened by selecting the monomolecular film formation conditions, such as the hydrogen ion intensity of the water tank, the ionic species, or the surface pressure.

In the recording medium of the present invention, an L-portion transparent support having a transparent electrode is provided on the monomolecular film or monomolecular cumulative film of the metal chelate compound described above.

The transparent support having a transparent electrode is, for example, SnO.

It may be a transparent electrode itself made of a vapor-deposited film such as 5n07, etc., or it may be a transparent electrode made of a vapor-deposited film such as 5n07 etc. on the surface of a transparent plate or film made of glass, plastic, etc. Examples include those in which a vapor-deposited film is formed. This transparent support may be placed by being pressure-bonded to the 1-distribution molecular film or monomolecular cumulative film, or
forming a monomolecular film or a monomolecular-cumulative film on a transparent support;
This may be integrally formed by pressure bonding with a monomolecular film or a monomolecular cumulative film formed on the photoconductive layer. The transparent electrode provided on the transparent support is preferably formed in direct contact with a monomolecular film or a monomolecular cumulative film of a metal chelate compound.

The recording principle using such a recording medium of the present invention will be explained below.

First, FIG. 1 is a schematic diagram showing the structure of a recording medium using a conventional metal chelate compound, and in FIG. 1a,
A reactive substance 4 such as a coordination r-1 reducing agent that causes a coloring reaction or the like to occur in the metal gillet 1, compound 3, and the chelate compound by the action of active energy is mixed and dispersed in a binder 5 on a support 11-. A recording medium layer 2 is formed and configured. Further, in FIG. 1b, a metal chelate compound 3 and a reactant 4 which react with each other are dispersed in a binder 5 in separate layers. This configuration causes the aforementioned problems such as increased layer thickness, lack of resolution of recorded images, and fog.

The recordability method using a medium according to the present invention is to apply light or the like as an active energy signal to the recording medium and apply an electric field to the recording medium, thereby recording the information in the recording medium at the active energy signal applying part. This method involves causing an electrolytic reaction in a metal chelate compound, reducing the metal ion in the metal chelate compound to the metal original f-, and creating a visible image. This is schematically shown in Figure 2. and FIG.

First, to explain the case shown in FIG. 2, a conductive support 17, a photoconductive layer 6, a metal chelate compound 3. When a recording medium formed by successively laminating a transparent electrode 7 and a transparent support 8 is irradiated with a light beam 9 of moderate light intensity, only the portion of the photoconductive layer irradiated with light becomes conductive, and the conductive support becomes conductive. body l
When an electric field is applied to the ml between and the transparent electrode 7 (Fig. 2a),
A strong electric field is applied between the conductive photoconductive layer and the transparent electrode 7, and the strength of the electric field is significantly different from the part that has not been irradiated with the light beam. The metal ions in the intermediate molecular film or monomolecular cumulative film of the metal chelate compound 3 in the portion where is applied, that is, the portion irradiated with light, are reduced, the metal 10 is separated by M, and a recorded image is formed by metal atoms. (Figure 2b).

FIG. 3 shows a modification of the recording medium used in FIG. It is configured by providing. The method of forming a recorded image is not completely different from that shown in FIG.

The main features of the recording medium of the present invention are summarized as follows.

(1) It is a recording medium that is extremely sensitive to energy signals.

(2) Since the recording layer is composed of the recording material, ie, the metal Kiri-1 and the compound China-Chinese, extremely high sensitivity can be achieved without adding distortion or noise to one image.

(3) Medium molecule reduction or φ molecule accumulation using LB method 11
Therefore, it is easy to refine the human aspect of the recording medium.

(4) Since the structure of the recording medium is simple and the amount of metal chelate compound used is small, it is excellent in productivity and economy.

Hereinafter, the recording medium of the present invention will be described in detail with reference to Examples.

Example 1 A chloroform solution (concentration: 1 x 1 O-3 mol%) of a metal chelate compound represented by the structural formula L was spread on the surface of water to form a medium molecular film of the compound on the water surface. An 8-layer intermediate molecular cumulative film was formed using the LB method on a glass plate on which a 5n07 transparent electrode was formed using the horizontal pricking method (surface pressure: 35 dyne/c).
m) On the other hand, a photoconductive polyvinyl lupinol/
A recording medium was formed by laminating trinitrofluorene films to a thickness of 5 tiles, and pressing these two monomolecular cumulative film layers of the glass substrate and the photoconductive layer into contact with each other. This record #! For the medium, the electrode on the cumulative film layer side is set to IF, and the electrode on the photoconductive layer side is set as negative, for about 10 minutes.
While applying a DC voltage of 0,
When light was irradiated with a 00W ultra-high pressure mercury lamp (light intensity IHs, eCoW/cm2), a black image due to silver atoms appeared only in the areas irradiated with light. b1) The resulting images were extremely sharp and had excellent resolution.

Example 2 A photoconductive resin coating consisting of titanium oxide fine powder dispersed in polyvinyl butyral resin at a weight ratio of 7:l +I' was applied to a glass plate on which a 5n07 transparent electrode was formed. was formed to a thickness of 5 capes.

In addition, a chloroform solution (concentration 5 x 10" mol%) of a metal compound represented by the structural formula L was placed on the surface of the water to form a medium molecule film of the L compound on the water surface. A monomolecular cumulative film of the middle layer was formed on the photoconductive resin coating of the glass plate I by the LB method using the water 11i adhesion method (surface pressure 30 dyne/c).
m). On the laminated surface of this monomolecular cumulative film, 5
A recording medium was formed by press-contacting a glass plate on which a transparent electrode of n02 was formed so that the electrode surface overlapped with the glass plate. This recording medium was irradiated with light while applying a DC voltage of approximately 100 V in the same manner as in Example 1, with the light irradiation electrode set to positive and the electrode on the photoconductive layer side set to negative. A black image due to silver atoms appeared only in the exposed areas. The images obtained were extremely sharp and had excellent resolution.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing the structure of a conventional recording medium using all bachelate compounds. Figures 2 and 3 are
1 is a schematic diagram showing the configuration of a recording medium of the present invention and the recording principle using this recording medium. 1: Support 2: Recording medium layer 3: Metal layer 1/Compound 4: Reactant 5/Binder 6
: Photoconductive layer 7: Transparent electrode 8: Transparent support 9: Light rays 10: Metal 11/electrode Figure 1a Figure 1b Figure 2a Figure 2b Figure 3a Figure 3b

Claims (1)

[Claims] l) Support (-) A recording medium comprising a transparent support supporting a photoconductive layer, a medium molecular film of a metal chelate compound or a transparent electrode, and a transparent electrode.