JPS61169873A - Image forming method - Google Patents

Abstract

PURPOSE:To execute easily production and recording without exercising special care for photosensitivity and to make possible the long-term stable preservation of an image by using a recording material formed with a specifically constituted recording layer and photosensitive layer on a conductive substrate. CONSTITUTION:The recording material 10 is formed by providing the recording layer 2 consisting of a colored electrolytically polymerized film on the conductive substrate 1 consisting of a metallic plate of gold, platinum, copper, etc. and depositing the photosensitive layer 3 constituted of a polymer complex composed of a basic polymer such as N-vinyl pyrolidone and acid polymer such as citric acid and a sensitizer thereon. An original is placed onto the material 10 and is exposed with active rays to form a latent image in the photosensitive layer 3. The material in such a state is immersed into an electrolyte 7 and electricity is conducted thereto to develop the image. The production and recording are thus easily executed without exercising special care for the photosensitivity and the long-term stable preservation of the image is made possible.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method of recording various information using patterns of actinic light to form a visible image.

More specifically, a recording layer with a specific configuration and a photosensitive layer with a specific configuration are formed on a conductive substrate, a latent image is formed in the photosensitive layer by a pattern of actinic light, and the latent image is utilized to It is an object of the present invention to provide a WjI image forming method in which a recording layer can be easily developed into a visible image by electrochemical means.

(Prior Art) Conventionally, there are many known methods for recording various types of information using patterns of actinic rays. A photosensitive layer with changing properties is provided on the
By applying a pattern of actinic light to these photosensitive layers, a visible change in the photosensitive layer or a recorded image readable by other reading means is formed. A photosensitive material is often used to form the photosensitive layer.
Many of these materials are various polymers, pigments, or mixtures thereof.

(Problems to be Solved by the Invention) For forming a photosensitive layer of a recording material used in the above-described conventional recording method using a pattern of actinic rays.

In many cases, photosensitive polymers and dyes are used, so when forming a photosensitive layer from these materials,
There is a problem in that sufficient care must be taken in handling these materials.

That is, in order to form photosensitive layers from materials that are sensitive to light, such as visible light or ultraviolet light, these materials must be made non-sensitized before use, and for similar reasons, storage of the recording material after formation must be ensured. If sufficient care is not taken, they will lose their photosensitivity before use, rendering them unusable.

Furthermore, even with such various precautions, conventional recording materials using actinic ray patterns have problems with the storage stability of recorded materials after recording, and are not sufficiently reliable in terms of long-term storage life. It wasn't something to give.

Therefore, there is a need for a recording material and a recording method that do not require special precautions during production, can easily form a photosensitive layer, can easily record information, and can stably store recorded information for a long period of time. The reality is that there is still a strong demand for it.

In order to meet the demands of the prior art as described above, the present inventors
As a result of extensive research, we have found that it is easy to use a conductive substrate as a supporting base for a recording material, to form a recording layer from a specific material, and to use a polymer material with a specific composition as a material constituting a photosensitive layer. Various types of information can be recorded using patterns of actinic rays, and furthermore, by using the latent image of the recorded information and making it into a visible image using specific electrochemical means, recorded images with excellent storage stability can be created. The present invention was completed after discovering that the present invention can be obtained.

(Means for solving the problems) That is, the present invention comprises a conductive substrate, a recording layer provided on the conductive substrate, and a photosensitive layer provided on the recording layer,
A recording material in which the recording layer is made of a colored electropolymerized film and the photosensitive layer is made of a polymer complex of a basic polymer and an acidic polymer and a sensitizer is exposed to actinic light to form a latent image, and then This is an image forming method that consists of immersing the recording material in an electrolytic solution and applying electricity to develop the exposed portion.

To explain the present invention in detail, the main features of the present invention are:
The first feature is that a conductive substrate is used as the substrate for the recording material used, the second feature is that the recording layer is formed of a specific colored polymer, and the third feature is that The fourth feature is that a specific polymer complex is used to form the photosensitive layer, and the fourth feature is that the recording material thus formed is exposed to a pattern of actinic light using a conventional method, and the latent The point is that electrochemical means were used to develop the image.

Therefore, the present invention will be further described in detail focusing on these main features.

The electrically conductive substrate used as the substrate of the recording material in the present invention may be any material as long as it is electrically conductive, such as metal plates such as gold, platinum, silver, nickel, copper, these metals, tin oxide, Any substrate having a conductive oxide such as indium oxide, indium-tin oxide, or other conductive material deposited on one or both sides of a glass plate, various resin films, or sheets can be used.

In the present invention, the recording layer provided on the substrate is formed by electrolytic polymerization. Such electrolytic polymerization is a method in which an electrolytically polymerizable top is added to an electrolytic solution and electrolytic polymerization is performed using a conductive substrate as an anode.

The electrolytic polymerization method preferably used in the present invention is 1.
971-974", but according to detailed research by the present inventor, it was found that such an electrolytic polymer film is suitable as the recording layer of the recording material in the present invention. It is something.

That is, when electricity is applied in an electrolytic solution containing a monomer for electrolytic polymerization using the above conductive substrate as an anode, electrolytic polymerization occurs on the surface of the anode, and a colored electrolytic polymer film is formed on the surface. , a recording layer with excellent performance is formed.

Examples of monomers used in such electrolytic polymerization include monomers such as pyrrole, thiophene, furan, selenophene, tellurophene, indole, azulene, aniline, chenothiophene, pyrrolovirol, and diacetylene. - is about o in the electrolyte,
It is preferable to use it at a concentration of about ooi to IM.

In addition, as the cathode which is the opposite electrode to the above anode, gold, platinum,
Any electrode material such as nickel may be used, and these cathodes may have any shape.

As the electrolytic solution, any conventionally known electrolytic solution such as water, acetonitrile, ethanol, dimethylformamide, dioxane, dichloroethane, and tetrahydrofuran can be used.
Br, K1. Any electrolyte can be used, such as LiCQO,, LiB%, tetra-n-butylammonium verchlorate, tetra-n-butylammonium perfluoroporate, tetramethylammonium chloride, Na, 504, etc., and these electrolytes are Approximately 0. O1~I
It is preferable to dissolve it at a concentration of about M.

Electrolytic polymerization conditions vary depending on the type of monomer used, the type and shape of the electrode, the type and concentration of the electrolytic solution and electrolyte, and the size of the recording surface of the conductive substrate used in the present invention, but are generally By applying a DC voltage of 1 to IOV to the conductive substrate, approximately 0.1 to 1OV is applied to the conductive substrate in a few seconds to several minutes.
A colored electropolymerized film, that is, a recording layer, having a thickness of p and m is formed.

The electropolymerized membrane formed as described above is generally strongly colored from brown to black depending on the type of electrolyte, but if the degree of coloring is small, anionic dyes such as acid dyes and direct dyes may be added to the electrolyte. By dissolving an appropriate amount of a pigment such as a dye having a group, the hue of the coloring can be changed or the density can be increased. Further, it goes without saying that coloring with such a dye may be performed after H is formed.

The polymer complex used to form the photosensitive layer on the recording layer on the substrate is composed of a basic polymer and an acidic polymer.
The basic polymer itself is already known in Japanese Patent No. 5-42744, and includes, for example, the following.

N-vinylpyrrolidone, N-vinyl-3-methylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinyl-3,3,5-trimethylpyrrolidone, N-vinyl-3
-Benzylpyrrolidone.

Homopolymers such as N-vinylpiperidone, N-vinyl-4-methylpiperidone, N-vinyl-caprolactam, N-vinylcapryllactam, N-vinyl-3-morpholine, N-vinylthiopyrrolidone, N-vinyl-2-pyridone, etc. Or random copolymers, block copolymers, graft copolymers, etc. with other common hexamers; N-vinyl-2-oxazolidone, N-vinyl-5-methyl-2-oxazolidone, N-vinyl -5-ethyl-
2-oxazolidone, N-vinyl-4-methyl-2-oxazolidone, N-vinyl-2-thioxazolidone,
Homopolymers such as N-vinyl-2-mercaptobenzothiazole or random copolymers, block copolymers, graft copolymers, etc. with other common heptadol; N-vinylimidazole, N-vinyl- Homopolymers such as 2-methylimidazole and N-vinyl-4-methylimidazole, or random copolymers, block copolymers, graft copolymers, etc. with other common heptadol; 2- or 4- Examples include homopolymers such as vinylpyridine, random copolymers, block copolymers, graft copolymers, etc. with other common monomers, and other copolymerizable polymers that may be used in the above. are methacrylate, acrylate, acrylamide, acrylonitrile, vinyl ether, vinyl acetate, vinylimidazole,
Ethylene, styrene, and other common monomers that are particularly useful in the present invention include N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylmorpholine, N-vinyl-2-oxazolidone, These include homopolymers and copolymers of N-vinyl-5-methyl-2-oxazolidone. In the case of a copolymer, it is preferable that the above-mentioned nitrogen-containing monomer is included in an amount of 50 mol % or more.

Further, examples of acidic polymers capable of forming a polymer complex with the above-mentioned basic polymers include the following.

Polyesters with terminal carboxyl groups obtained by reacting polyhydric carboxylic acids such as citric acid, tartaric acid, and heptallic acid with polyhydric alcohols such as ethylene glycol, 1.4-butanediol, and diethylene glycol in excess of acid; various polyhydric carboxylic acids. Acidic cellulose derivative modified with acid (
(Refer to Japanese Patent Publication No. 35-5093): Homopolymers such as vinyl ether ester monomers of polyhydric carboxylic acids, random copolymers with other common heptamers, block copolymers, graft copolymers, etc. Tokuko Sho 35-8495
Homopolymers of heptamers such as acrylic acid or methacrylic acid or random copolymers with other common heptamers;
Block copolymers, graft copolymers, etc.: Random copolymers, block copolymers, homopolymers of α,β-unsaturated vinyl humers such as maleic anhydride, itaconic acid, or other common monomers; Graft copolymers, etc.: Homopolymers of heptamers containing other sulfonic acid or phenol groups, or random copolymers with other general heptamers, block copolymers, graft copolymers, etc.; Others Acidic modified products of various polymers with compounds containing carboxyl groups, sulfonic acid groups, or phenol groups: Any of the above acidic polymers can be used, but particularly preferred in the present invention are α,β-unsaturated acids. These include homopolymers, random copolymers, block copolymers, and graft copolymers, and particularly preferred are copolymers of alkyl vinyl ether and maleic anhydride.

The present inventor has been conducting various research on mixtures of basic polymers and acidic polymers as described above, and found that
By mixing these polymers in a solution, both polymers interact in some way to form a polymer complex that is different from either polymer,
If both polymers are mixed in a relatively good solvent, a polymer complex will precipitate, and if mixed in a relatively good solvent, a significant increase in viscosity will occur, resulting in properties different from those of a simple mixture of both polymers used. This is what we have discovered.

Therefore, the polymer complex used in the present invention means a polymer complex consisting of the above-mentioned polymers. In the present invention, it is preferable to use both polymers in such a manner that their basicity and acidity are approximately the same. The mixing ratio can be determined by calculating the basicity 2 and acidity of the two polystyrene, and determining the mixing ratio of the two accordingly. Furthermore, a polymer complex formed by mixing in an appropriate ratio becomes a polymer complex that cannot be strongly dyed by either acidic dyes or basic dyes. Therefore, the mixing ratio of both polymers can be determined using these factors.

Since the polymer complex obtained as described above is generally not soluble in relatively poor solvents such as water, alcohol, ester, hydrocarbon, etc., both polymers are dissolved in these poor solvents and 1 By mixing both solutions, the polymer complex used in the invention can be isolated. Alternatively, a solution of the polymer complex can be obtained by mixing in a relatively good solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, or the like. Therefore, when forming a photosensitive layer on a conductive substrate as described above using a polymer complex as described above, (1) Prepare solutions of both polymers,
A method in which one of the solutions is applied onto the recording layer on the substrate, and then a predetermined amount of the other polymer solution is applied thereon to form a polymer complex on the recording layer. A method can be used in which a solution of the polymer complex is prepared using a good solvent and the solution is applied onto the recording layer.

In forming the photosensitive layer as described above, a conventionally known photosensitive material (sensitizer) is included in an appropriate amount, for example, about 0.1 to 10 parts by weight per 100 parts by weight of the polymer complex. It is necessary to impart photosensitivity to the material. As such sensitizers, conventionally known ones 1
For example, spiropyran compounds, anthrone compounds, triphenylmethane compounds, and other organic photochromic materials; photosensitive aromatic diazonium compounds, particularly preferably diazonium double salts soluble in organic solvents; aromatic azide compounds: polyhalogen-containing Compounds: Other photodegradable compounds can optionally be used. These sensitizers themselves are already known, and are specifically disclosed in, for example, Japanese Patent Publication No. 55-42744.

The recording material used in the present invention is formed using one or more of the above materials, but in the present invention, in addition to the above materials, for example, a thermoplastic polymer other than the above may be used in combination with the above polymer complex. They may enhance their film-forming ability, or they may include small amounts of colorants to give their films a light color.

Next, the present invention will be described in more detail with reference to the accompanying drawings that schematically illustrate the structure of the recording material used in the present invention. FIG. 1 schematically shows the structure of the recording material 10 of the present invention with its cross-sectional shape, where l represents the conductive substrate as described above, 2 represents the recording layer, and 3 represents the polymer. FIG. 2 is a schematic cross-sectional view of a recording material of another example, showing a photosensitive layer consisting of a complex and a sensitizer.

As shown in FIGS. 1 and 2, 1 recording material 10 used in the present invention
In this method, a recording layer 2 made of an electrolytically polymerized film is formed on at least one surface of a conductive substrate 1, and a photosensitive layer 3 made of the above-mentioned polymer complex and a sensitizer is further formed thereon. As shown in FIG. 2, if the recording layer 2 and the photosensitive layer 3 are formed on both sides of the conductive substrate 1, the recording layer 2 and the photosensitive layer 3 can be formed on both sides.
The recording material 10 has the following properties. Recording layer 2 only on one side
When forming the photosensitive layer 3, it is preferable to apply an insulating coating (not shown) of any thickness to the other surfaces, most preferably to the conductive substrate itself.

This is not necessary when the substrate is conductive on one side, such as ITO-deposited glass or aluminum-deposited film.

The conductive substrate 1 used can technically have any thickness and any shape, but generally has a thickness of about 0.0
A plate-like, sheet-like, or film-like form with a thickness of 3 to 3 layers is preferable, and its shape may be any shape, such as a tape-like shape, depending on the purpose of use of the recording material obtained. It may have the same shape or a smaller area, and the thickness is generally preferably about 001 to 10 ILm. The photosensitive layer 3 may be formed using either the L-liquid method or the Z-liquid method as described above, but the preferred thickness is generally about 0.1 to 104 m.

The present inventor discovered that the recording material formed as described above becomes a poor conductor as a whole and loses good conductivity, although the substrate 1 and the recording layer 2 are conductive. Ta. This was naturally predicted since the 211 polymers constituting the polymer complex forming the photosensitive layer 3 were mutually neutralized, but further detailed research by the present inventor revealed that When these photosensitive layers are exposed to a pattern of actinic light having energy greater than the surrounding atmosphere, only that portion of the photosensitive layer becomes conductive again, that is, a latent image consisting of conductive areas is formed. This is what we discovered. Furthermore, such a latent image retained its electrical conductivity for several minutes to several days even after application of the actinic light pattern was discontinued, and thereafter returned to its original insulating property.

As for the method of recording information and forming a latent image by exposing the above-mentioned recording material to a pattern of actinic rays, any conventionally known method can be used. Another method uses light 4 as a recording means, and overlaps a transparent original 5 having an image pattern with a recording material 1O, or forms an image of the pattern of the original on a photosensitive layer of the recording material through a lens system ( (not shown) etc. can be used arbitrarily. The actinic rays used here are:

Ultraviolet rays, visible rays, infrared rays, these laser beams, electron beams, etc. can be used.

As described above, a desired latent image is formed in the photosensitive layer of the recording material used in the present invention, but the recording material of the present invention can be developed into a visible image in the following manner. The development method is also an important feature of the invention.

A method for developing the latent image formed as described above will be specifically explained with reference to the accompanying drawings. FIG. 4 schematically shows a method for developing the latent image 6 formed on the recording material used in the present invention, and FIG. 5 schematically shows a cross section of the developed recording material IO. This is what is shown.

As shown in FIGS. 4 and 5, one preferred method for developing is to soak the recording material 1O on which these latent images have been formed in an electrolyte solution 7.
As a result, only the latent image area becomes conductive due to zero current application, which is a method of immersing it as an anode in the liquid and applying current.As a result, the electrolytic polymer film, which is the recording layer corresponding to the latent image area, becomes colorless due to electrochemical action. becomes. Although the mechanism of this colorlessness is not clear, it is thought that the conjugated system in the electrolytically polymerized film, which is the recording layer, is oxidized and cleaved by anodic oxidation during one energization, resulting in colorlessness. Furthermore, when a dye anion is present in the polymer film, it is thought that the dye is similarly oxidized and decomposed to become colorless. In this way, a high contrast negative pattern is formed. Moreover, if the non-image area is exposed and developed in the same manner as above, it is natural that a positive pattern will be formed. Furthermore, another method for obtaining a positive image is to pass through the steps of imparting a light pattern in the form of an image, developing it using the recording material as a cathode, then immediately converting the recording material to an anode and developing it. Another major feature of the present invention is that the non-image area becomes colorless and a positive image is obtained.

In addition, the electrolytic solution 7 and the cathode in the above development process may be the same as the electrolytic solution and the cathode in the electrolytic polymerization,
Further, the developing conditions may be the same.

As explained above in detail, the image forming method of the present invention involves forming a recording layer made of an electrolytically polymerized film on a conductive substrate, and further depositing a specific photosensitive polymer complex on top of the recording layer.
A material with a photosensitive layer formed thereon is used, and the formed recording layer and photosensitive layer do not lose their photosensitivity at all even if left in a normal atmosphere, and the recording layer and photosensitive layer are 1. In forming the layer, there is no need to pay special attention under normal atmosphere, so the production is industrially advantageous, and the formed latent image can be easily processed by electrolytic treatment. Developed into a high-contrast image. In addition, after development, the area where the latent image was and other areas of the photosensitive layer return to the same state as the stable polymer complex before recording over time, and the photosensitive layer as a whole or partially changes depending on the ambient conditions. The storage stability of the recorded information is extremely excellent because the information does not change.

Next, the present invention will be explained in more detail with reference to Examples.

Note that "%" or "%" in the middle of the sentence is based on weight.

Example 1 0.1 M of virol and 0.1 M of sodium P-)luenesulfonate were dissolved in water to prepare an electrolytic polymerization solution. An ITO glass plate with a resistance of 20 Ω and a size of 10 x 10 cm was inserted as an anode, and a nickel plate was used as a cathode. Electrolysis was performed at a DC voltage of 3 V for 50 seconds to form a greenish-brown conductive polypyrrole film (thickness of about 1 #Lm). ) was formed on the anode.

Polyvinylpyrrolidone (K=90) 5 parts Methyl vinyl ether/maleic anhydride-monobutylnistil copolymer (Gantret ES-425, 50% ethanol solution, manufactured by GAF) 10 parts P-N
, N'-dimethylaminobenzene-diazonium tetrafluoroboilete 0.5 parts Ethanol 100 parts Dimethylformamide 100 parts The above mixture was uniformly applied onto the polypyrrole film using a Meyer's bar (#32). , and dried at 100° C. for 5 minutes to form a photosensitive layer with a thickness of 3 pm, thereby obtaining a recording material used in the present invention.

A negative pattern made of silver salt was attached to this, and light from a high-pressure mercury lamp (400 W) was irradiated from the pattern side for about 3 seconds (distance 10 cm).

Next, this was connected to the anode of a DC power supply, a nickel plate was connected to the cathode, and constant voltage electrolysis (4V, 10 seconds), the portion corresponding to the exposed portion faded and became colorless, and an image of a negative pattern corresponding to the negative pattern used with a greenish-brown background color was formed. The obtained image had a high contrast and could be used as a slide, and the storage stability of the obtained image was very good, and the film had sufficient adhesion to the substrate.

Example 2 In the polymer solution for the recording layer used in Example 1, P
-N, N'-dimethylamide benzene di
゛Instead of azonium tetrafluoroborate, 6'-
Nitrospirobilane was used to coat a polypyrrole film in the same manner as in Example 1 to obtain a recording material having a photosensitive layer with a thickness of 2 ILm. After pattern exposure was performed using a high-pressure mercury lamp in the same manner as in Example 1 (exposure time: 5 seconds), this recording material was connected to the anode of a DC power source, a nickel plate was connected to the cathode, and 0.1M P- ) When constant voltage electrolysis (4V, 10 seconds) was performed in an electrolytic solution of 100 parts of water containing sodium luenesulfonate, the areas exposed to light became colorless, resulting in a colorless and transparent negative pattern on a brown background. was obtained with high contrast.

Example 3 A recording material prepared in exactly the same manner as in Example 1 was imagewise exposed to light using a high-pressure mercury lamp (400 W) in the same manner as in Example 1, and then exposed to light in a 0.1 M aqueous solution of sodium P-)luenesulfonate as described above. When the recording material was connected to the anode and the nickel plate was connected to the cathode and a DC voltage of 4 V was applied for 10 seconds, the non-exposed areas were brown and the exposed areas were colorless, forming a positive pattern. The images obtained have sufficient contrast and
It was useful for slides, masks, optical discs, etc.

[Brief explanation of the drawing]

1 and 2 schematically show the structure of a recording material used in the present invention, FIG. 3 schematically shows exposure in the method of the present invention, and FIG. 4 schematically shows development in the method of the present invention. The method is illustrated diagrammatically, and FIG. 5 diagrammatically depicts the developed recording material. 1... Conductive base material 2... Recording layer 3... Photosensitive layer 4... Actinic light 5... Original 6...・・・
・Latent image 7... Electrolyte 8...
・Image 9...Cathode 1j...
・Recording material patent applicant: Canon Corporation Figure 1 IJIc3 Figure 4

Claims (1)

[Claims] It consists of a conductive substrate, a recording layer provided on the conductive substrate, and a photosensitive layer provided on the recording layer, wherein the recording layer is made of a colored electrolytic polymer film, and the photosensitive layer is made of a basic polymer and an acidic polymer. A recording material made of a polymer complex and a sensitizer is exposed to actinic rays to form a latent image, and then the recording material is immersed in an electrolytic solution and current is applied to develop the exposed areas. Formation method.