JPS61169852A - Image recording material - Google Patents

Abstract

PURPOSE:To execute 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 base. CONSTITUTION:The image recording material 10 is constituted by forming the recording layer 2 consisting of a colored electrolytically polymerized film on the conductive substrate 1 and forming further the photosensitive layer 3 consisting of a polymer complex composed of a basic polymer and acidic polymer and a sensitizer thereon. The recording is executed by placing an original onto the material 10 and exposing the same with active rays to form a latent image then immersing the material into an electrolyte and conducting electricity thereto to develop the image. The recording layer 2 and the photosensitive layer 3 do not lose the photosensitivity even after resting in an ordinary atmosphere and no special care is required in the stage of production. The recording is easy and the polymer complex is stable after development. The long-term stable preservation of the image is thus realized.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to an image recording material useful for recording various information using patterns of actinic rays and forming visible images. A recording layer with a specific configuration and a photosensitive layer with a specific configuration are formed on a transparent substrate, a latent image is formed in the photosensitive layer by a pattern of actinic rays, and the latent image is used to perform recording by electrochemical means. The object is to provide an image recording material whose layers can be easily developed into a visible image.

(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.

(Problem to be solved by the invention) In many cases, photosensitive polymers and dyes are used to form the photosensitive layer of image recording materials used in the conventional recording method using patterns of actinic rays as described above. Therefore, 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, those materials must be made non-sensitized before use, and for similar reasons, storage of image-recording materials after formation is difficult. has the problem that, unless more care is taken, it loses its photosensitivity before use, rendering it unusable.

Furthermore, even with such various precautions, conventional image recording materials based on actinic light 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 was not intended to give.

Therefore, there is no need to take special precautions during production, an image recording material and a recording method in which a photosensitive layer can be easily formed, information can be easily recorded, and the recorded information can be stably stored for a long period of time. The reality is that there is still a strong demand for this.

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 when a conductive substrate is used as a support base for an image recording material, a recording layer is formed from a specific material, and a polymer material with a specific configuration is used as a material constituting a photosensitive layer, Various types of information can be easily recorded using actinic light patterns, 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,
The image recording material is an image 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.

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 of the image recording material, the second feature is that the recording layer is formed of a specific colored polymer, and the third feature is that The point is that a specific polymer complex is used to form the photosensitive layer.

The image recording material of the present invention thus formed is exposed to a pattern of actinic rays in a conventional manner to form a latent image, and the resulting latent image can be easily developed by electrochemical means. can be done.

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

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

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 monomer is added to an electrolytic solution and electrolytically polymerized using a conductive substrate as an anode.

The electrolytic polymerization method used in the present invention is, for example, “
Applied Physics, Vol. 52, No. 11 (11183) P971
Although it is known per se as in "-974", 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 image recording material in the present invention. It is something.

That is, when the above-mentioned conductive substrate is used as an anode and electricity is applied in an electrolytic solution containing a 7-mer for electrolytic polymerization, 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 seven monomers such as pyrrole, thiophene, furan, selenophene, tellurophene, indole, azulene, aniline, chenothiophene, pyrrolopyrrole, and diacetylene. is about 0.0 in the electrolyte.
It is preferable to use it at a concentration of about 001 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.
r, KI, Li0 sentence 04, Li B F4, Tetra-
n-butylammonium verchlorate, tetra-n-
Butylammonium perfluoroporate, tetramethylammonium chloride, Na, So. Any electrolyte can be used, and these electrolytes are preferably dissolved at a concentration on the order of about 0.01 to LM.

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 l~IOV to the conductive substrate in a few seconds to several minutes, approximately
A colored electropolymerized film, ie, a recording layer, having a thickness of ILm 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.

You can change the hue of the coloring or increase the density.

Furthermore, it is also possible to carry out coloring with such a dye after forming the film.

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 examples of the basic polymer include the following.

N-vinylpyrrolidone, N-vinyl-3-methylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinyl-3,3,5-trimethylpyrrolidone, N-vinyl-3
-Benzylpyrrolidone, N-vinylpiperidone, N-vinyl-4-methylpiperidone, N-vinyl-caprolactam, N-vinylcapryllactam, N-vinyl-3
- Homopolymers of morpholine, N-vinylthiopyrrolidone, N-vinyl-2-pyridone, etc. or random copolymers, block copolymers, graft copolymers, etc. with other common heptamers; 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 and block copolymers with other common monomers.

Graft copolymers, etc.; Examples include homopolymers such as 2- or 4-vinylpyridine, random copolymers with other common monomers, block copolymers, graft copolymers, etc. Other copolymerizable polymers that may be used include methacrylate, acrylate, acrylamide, acrylonitrile, vinyl ether, vinyl acetate, vinylimidazole,
Ethylene, styrene and other common heptamers, among others, are particularly useful in the present invention: N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylmorpholine, N-vinyl-2-oxazolidone. , a homopolymer, a copolymer of N-vinyl-5-methyl-2-oxazolidone, and the like. 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 that can form a polymer complex with the above basic polymer include the following.

Polyesters with terminal carboxyl groups obtained by reacting polycarboxylic acids such as citric acid, tartaric acid, and phthalic acid with polyhydric alcohols such as ethylene glycol, 1,4-butanediol, and diethylene glycol in excess of acid; various polycarboxylic acids Acidic cellulose derivative modified with (
Homopolymers such as vinyl ether ester monomers of polyvalent carboxylic acids, random copolymers, block copolymers, graft copolymers, etc. with other common monomers (see Japanese Patent Publication No. 35-5093); 35-8495
(Refer to the publication No. 2002-12-13); A heptamer homopolymer such as acrylic acid or methacrylic acid or a random copolymer with other common monomers,
Block copolymers, graft copolymers, etc.; homopolymers of α,β-unsaturated vinyl humers such as maleic anhydride and itaconic acid, or random copolymers and block copolymers with other common monomers; Graft copolymers, etc.; Homopolymers of monomers containing sulfones or phenol groups, or random copolymers, block copolymers, graft copolymers, etc. with other common monomers; Other carboxyl groups or sulfones. Acidic modified products of various polymers with compounds containing acid groups or phenol groups; Although any of the above acidic polymers can be used, particularly preferred in the present invention are homopolymers of α,β-unsaturated acids. , random copolymers, block copolymers, and graft copolymers, and particularly preferred is a copolymer 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 and acidity of both polymers, and determining the mixing ratio of both polymers 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 good solvents such as water, alcohol, ester, hydrocarbon, etc., both polymers are dissolved in these poor solvents, respectively. By remixing the solution, the polymer complex used in the present 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,
(2) A method of applying one of the solutions onto the recording layer on the substrate, and then applying a predetermined amount of the other polymer solution 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. Such sensitizers include conventionally known ones,
For example, spiropyran compounds, anthrone compounds, triphenylmethane compounds, other organic photochromic materials: photosensitive aromatic diazonium salt compounds, particularly preferably diazonium double salts soluble in organic solvents: aromatic azide compounds; polyhalogens Containing compounds: Other photodegradable compounds can be used arbitrarily. These sensitizers themselves are already known, and are specifically disclosed in, for example, Japanese Patent Publication No. 55-42744.

The image recording material of the present invention is formed using the above-mentioned materials, but in the present invention, in addition to the above-mentioned materials, for example, a thermoplastic polymer other than the above-mentioned materials may be used in combination with the above-mentioned polymer complex. Small amounts of colorants may be included to enhance their film-forming ability and 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 image recording material of the present invention.

FIG. 1 schematically shows the structure of the image recording material 10 of the present invention by its cross-sectional shape, where 1 represents the conductive substrate as described above, 2 represents the recording layer, and 3 represents the polymer complex. and a sensitizer.
The figure is a schematic cross-sectional view of an image recording material of another example.

As shown in FIGS. 1 and 2, the image recording material 1O used in the present invention has a recording layer 2 made of an electropolymerized film formed on at least one surface of a conductive substrate 1, and a recording layer 2 made of an electrolytic polymer film on which the above-mentioned polymer complex is further added. and a sensitizer. As shown in FIG. 2, by forming a recording layer 2 and a photosensitive layer 3 on both sides of a conductive substrate 1, an image recording material 1O having a recording layer 2 and a photosensitive layer 3 on both sides is obtained. When the recording layer 2 and photosensitive layer 3 are formed only on one surface, it is preferable to apply an insulating film (not shown) of an arbitrary thickness to the other surface. This is not necessary when the substrate is conductive on one side, such as ITO-deposited glass or aluminum-deposited film.

The conductive substrate l used can technically have any thickness and any shape, but generally has a thickness of about 0.0
It is preferably in the form of a plate, sheet, or film with a thickness of 3 to 3 cm, and the shape may be any shape, such as a tape shape, depending on the intended use of the image recording material obtained.
The recording layer 2 may have the same shape as the substrate 1 or may have a smaller area than the substrate 1, and its thickness is generally preferably about 0.1 to 10 gm. The photosensitive layer 3 may be formed by a one-liquid method or a two-liquid method as described above, but the thickness thereof is generally preferably about 0.1 to 10 JLm.

The present inventor discovered that although the image recording material formed as described above has a substrate 1 and a recording layer 2 that are electrically conductive,
It has been found that the material becomes a poor conductor as a whole and loses good electrical conductivity. This was naturally predicted since the two types of polymers constituting the polymer complex forming the photosensitive layer 3 were mutually neutralized, but the inventor's more detailed research revealed that this was the case. Therefore, 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, i.e., a latent image consisting of conductive areas is formed. This is what I found out. 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.

Any conventionally known method can be used to record information by exposing the image recording material as described above to a pattern of actinic rays to form a latent image.

For example, as schematically shown in FIG. 3, light 4 is used as a recording means, and a transparent original 5 having an image pattern is overlapped with an image recording material lO, or the pattern of the original is recorded through a lens system. Any method such as forming an image on the photosensitive layer of the image recording material (not shown) can be used. The active rays used here include ultraviolet rays, visible rays, infrared rays,
These laser beams, electron beams, etc. can be used.

As described above, a desired latent image 6 is formed in the photosensitive layer of the image recording material of the present invention, but the image recording material of the present invention can be developed into a visible image as follows. Such a developing method is also an important feature of the present invention.

A method for developing the latent image formed as described above will be specifically explained with reference to the accompanying drawings. FIG. 4 diagrammatically shows a method for developing the latent image 6 formed on the image recording material used in the present invention, and FIG. 5 diagrammatically shows a cross section of the developed image recording material 10. This is what is shown.

As shown in FIGS. 4 and 5, one preferred method for developing is to immerse the image recording material 10 on which these latent images have been formed as an anode in an electrolytic solution 7, and then energize the material 10. Since only the latent image area is conductive, the electrolytic polymer film, which is the recording layer corresponding to the latent image area, becomes colorless due to electrochemical action. 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 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.

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 in detail above, the image recording material of the present invention has a recording layer made of an electrolytically polymerized film formed on a conductive substrate, and further a specific photosensitive polymer complex formed on the recording layer.
A photosensitive layer is formed, and the formed recording layer and photosensitive layer do not lose any photosensitivity even if left in a normal atmosphere, and the recording layer and photosensitive layer are formed. The production process is industrially advantageous because there is no need to pay special attention under normal atmosphere, and the formed latent image can be easily produced with high contrast by just electrolytic treatment. Developed into an 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 pyrrole 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 placed as an anode, and a nickel plate was used as a cathode, and electrolysis was carried out at a DC voltage of 3 V for 50 seconds to form a green-brown conductive polypyrrole film (about 1 x m thick). was formed on the anode.

Polyvinylpyrrolidone (K=90) 5 parts Methyl vinyl ether/maleic anhydride-monobutyl nistyl copolymer (Gantretz E, S-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 evenly applied onto the polypyrrole film using a Meyer's bar (#32). , and was dried at 100° C. for 5 minutes to form a photosensitive layer with a thickness of 3 gm, thereby obtaining an image recording material of 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 (4 V, 10 As a result, the area corresponding to the exposed area faded and became colorless, forming a negative pattern image with a greenish-brown background color. 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'-Dimethylamidebenzenediazonium tetrafluoroporate was replaced with 6'-nitrospiropyran, and the same method as in Example 1 was used to coat the polypyrrole film to form a photosensitive layer with a thickness of 2 JLm. An image recording material of the present invention was obtained. This was subjected to pattern exposure using a high-pressure mercury lamp in the same manner as in Example 1 (exposure time: 5
seconds), connect this image recording material to the anode of a DC power source,
When a nickel plate was connected to the cathode and constant voltage electrolysis (4V, 10 seconds) was performed in an electrolyte of 100 parts of water containing 0.1M sodium p-toluenesulfonate, the area exposed to light was It became colorless, and a colorless and transparent negative pattern with high contrast was obtained on a greenish-brown background.

[Brief explanation of drawings]

1 and 2 schematically show the structure of the image recording material of the present invention, FIG. 3 schematically shows the exposure in the present invention, and FIG. 4 schematically shows the developing method in the present invention. and FIG. 5 schematically shows the developed image 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 Upper tongue...
・Image recording material Figure 1 Figure 2 Figure 3 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. An image recording material consisting of a polymer complex and a sensitizer.