JP2576906B2 - Image forming material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial application field" The present invention relates to copiers, faxes, printers, labels,
The present invention relates to a novel image forming material that can be used for applications such as a color proof, an overhead projector, and a second original drawing. In particular, the present invention relates to an image forming material using a novel dye bleaching method.

More specifically, it relates to a novel image forming material containing a photobleachable dye and an organoaluminum compound anion.
Further, the present invention relates to a novel mono-sheet type image forming material which does not use unnecessary consumables.

"Prior art" Various materials are known as image forming materials.
For example, a silver halide photographic material, a material using a photopolymer (for example, a printing material for flat plate and letterpress), a diazo photographic material, and an image forming material using a photo-bleaching method of a dye are known.

Among these materials, the image forming material using the photobleaching method of the dye, which obtains an image by photobleaching the dye in the image-exposed portion, is simple in image forming method, and can easily form an image only by dry processing. In principle, colorization is easy.

As a method for photobleaching a dye, a method using an organic boron compound is known. For example, British Patent No. 1,386,269, British Patent No. 1,370,058, British Patent No. 1,370,059, British Patent No. 1,370,060 and U.S. Patent No. 4,307,182 describe a combination of an organic boron compound and a bleachable dye. . Combinations of these organic boron compounds and bleachable dyes can easily form images directly by light.

Further, various ideas have been devised for photosensitive materials using the combination of the organic boron compound and a bleachable dye.
For example, U.S. Pat.No. 4,307,182 discloses a method of fixing an image as a fixing method of an image, and, for example,
EP 109,772 discloses a method for fixing with UV light. Further, U.S. Pat. No. 4,405,227 discloses a method in which a combination of these organic boron compounds and a bleachable dye is dispersed in a binder to reduce the amount of a solvent or to provide a color.

"Problems to be Solved by the Invention" However, despite these various efforts, organic boron compounds are generally expensive, so that their industrial use is limited.

A first object of the present invention is to provide an image forming material which uses a system in which a dye is bleached by exposure and which is designed so that a less expensive material can be used.

A second object of the present invention is to provide an image forming material which can obtain an image by a simple operation of only performing image exposure and which is designed so that a less expensive material can be used.

A third object is to provide a mono-sheet type image forming material which does not use unnecessary consumables and which is designed so that a less expensive material can be used.

"Means for Solving the Problem" As a result of intensive studies, the present inventors have found a less expensive compound using aluminum as a starting material. That is, the object of the present invention has been attained by an image forming material characterized in that a composition layer containing an organic aluminum compound anion and a photobleachable dye is provided on at least one surface of a support.

Preferred organoaluminum compound anions that can be used in the present invention are represented by the following general formula (I).

General formula (I) Here, R1, R2, R3 and R4 may be the same or different, and include an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkaryl group, a substituted alkaryl group, and an alkenyl group. A substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an alicyclic group, an aryloxy group, a substituted aryloxy group, an arylthio group, a substituted arylthio group, an arylamino group, a substituted arylamino group, an arylseleno group, a substituted arylserno group, A group selected from a heterocyclic group and a substituted heterocyclic group; R1, R2, R3 and R4 may have a cyclic structure in which two or more groups are bonded.

Further, at least one of R1, R2, R3 and R4 is represented by the general formula (II), the general formula (III) or the general formula (IV)
It is preferably a group represented by

General formula (II) -X-R5 General formula (III) General formula (IV) Here, X represents an oxygen atom, a sulfur atom, or a selenium atom; R5 is a group selected from an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, and a substituted heterocyclic group; R6, R7 Is a group selected from an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group and a substituted heterocyclic group; in the case of the structure of the general formula (III), R6, R6
One of 7 may be a hydrogen atom, or may have a cyclic structure bonded to each other.

Although it is possible to obtain an image-forming material by a photopolymerization reaction using a composition containing a salt of an organoaluminum compound anion having this structure and a radically polymerizable compound, the image-forming material of the present invention is obtained by photobleaching a dye. It utilizes a reaction, and a radical polymerizable compound is not an essential component.

As the photobleachable dye, a cationic dye or a nonionic dye is preferable.

When a cationic dye is used, it can be used as a counter ion of an aluminum compound anion.

In this case, examples of the organic cationic dye include cationic methine dyes and polymethine dyes: preferably, cyanine dyes, hemicyanine dyes, styryl dyes, and azamethine dyes; and more preferably, at least one indolenine skeleton or benzene. A dye having a selenazole skeleton. Carbonium dyes: preferably triarylmethane dyes. Pyrylium compounds: preferably pyrylium dyes and thiapyrylium dyes. Quinone imine dyes: preferably azine dyes, thiazine dyes, and oxazine dyes. Xanthene dye: preferably a rhodamine dye. Acridine dye. Azulenium dye. One or a combination of dyes selected from the above can be used.

In the present invention, commercially available products or the above-mentioned organic cationic dyes known in the industry can be further used. Examples of these dyes include, for example, the section on basic dyes in the Handbook of Dyes, edited by The Society of Organic Chemistry, and "Theory of Photographic Processes" by Tay Etchi-James, McMillan Publishing Company (THJames, "The T
heory of the Photo-graphic Process '' Macmillan Pub
lishing Co., Inc.), pages 194 to 290 in 1977, and pages 1 to 32 and 189 to 189 of "Chemistry of Functional Dyes" (CMC Publishing Company, 1981).
Pages 206 and 401 to 413, JP-A-59-189340, European Patent No. 223587A1, and the like can be referred to.

Among the above dyes, dyes particularly useful in the present invention are cyanine dyes and xanthene dyes. Specific examples of the cyanine dye useful in the present invention include a dye represented by the following general formula (V).

General formula (V) In the formula, Z1 and Z2 are heterocyclic nuclei usually used for cyanine dyes, in particular, thiazole nuclei, thiazoline nuclei, benzothiazole nuclei, naphthothiazole nuclei, oxazole nuclei, oxazoline nuclei, benzoxazole nuclei, naphthoxazole nuclei, tetrazole nuclei, pyridine nuclei , A quinoline nucleus, an imidazoline nucleus, an imidazole nucleus, a benzimidazole nucleus, a naphthoimidazole nucleus, a selenazoline nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus or an indolenine nucleus.
These nuclei include a lower alkyl group such as a methyl group, a halogen atom, a phenyl group, a hydroxyl group, a C1-4
May be substituted by an alkoxy group, carboxyl group, alkoxycarbonyl group, alkylsulfamoyl group, alkylcarbamoyl group, acetyl group, acetoxy group, cyano group, trichloromethyl group, trifluoromethyl group, nitro group, etc. Good.

L1, L2 or L3 represents a methine group or a substituted methine group. Examples of the substituted methine group include a lower alkyl group such as a methyl group and an ethyl group, a phenyl group, a substituted phenyl group, a methoxy group,
Examples include a methine group substituted with an aralkyl group such as an ethoxy group and a phenethyl group.

When L1 and R13, L3 and R14, and m1 = 3, L2 and L2 may be alkylene-bridged to form a 5- or 6-membered ring.

R13 and R14 are a lower alkyl group (more preferably an alkyl group having 1 to 8 carbon atoms), a carboxyl group, a sulfo group,
An alkyl group having a substituent such as a hydroxyl group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or a substituted phenyl group (preferably, the alkylene moiety is C1 to C5). For example, β-sulfoethyl, γ-sulfopropyl, γ-sulfobutyl, δ-sulfobutyl, 2- [2-
(3-sulfopropoxy) ethoxy] ethyl, 2-hydroxysulfopropyl, 2-chlorosulfopropyl, 2
-Methoxyethyl, 2-hydroxyethyl, carboxymethyl, 2-carboxyethyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoroethyl, allyl (a
llyl group) and other substituted alkyl groups commonly used for N-substituents of cyanine dyes. m1 represents 1, 2, 3 or 4. A- represents an anion of the aluminum compound of the structural formula (I).

Specific examples of the xanthene dye useful in the present invention include a dye represented by the following general formula (VI).

General formula (VI) R21, R22, R23, and R24 each independently represent a hydrogen atom, a carbon atom, an alkyl group or an aryl group having 1 to 6 carbon atoms, A- represents an aluminum compound anion of the structural formula (I), and Y represents hydrogen. Represents an atom, an alkyl group, an aryl group or an alkali metal.

As the photobleachable dye, a nonionic dye may be used. Nonionic dyes include merocyanine dyes, coumarin dyes, xanthene dyes, and thioxanthene dyes. Examples of nonionic dyes include, for example, "Theory of photographic processes" by T.E.T.J.James.
Macmillan Publishing Company (TH James's "The Theory of the
Photo-graphic Process, Macmillan Publishing Co.,
Inc.) 1977, pp. 194-290, "Functional Dye Chemistry"
(CMC Publishing Company, 1981), pages 1-32, 243-266 and 403
405 pages etc. can be referred to.

Further, for example, nonionic dyes described in JP-A-1-138204, 3-ketocoumarin compounds described in JP-A-58-15503, JP-B-59-28328,
No. 60-53300, naphthothiazole merocyanine compounds described in JP-B-61-9621, JP-B-62-3842, JP-A-59-89303, and merocyanine compounds described in JP-A-60-60104. Known nonionic dyes such as those described above can be used.

When a nonionic dye is used as the photobleachable dye, it is preferable to use a cationic compound as a counter ion of the aluminum compound anion.

As such a cationic compound, an organic cationic compound is preferable, and in addition to the above-mentioned cationic dye, a quaternary ammonium salt is preferable.

This quaternary ammonium salt may be used in combination with a cationic dye.

As the organic aluminum compound anion represented by the general formula (I), an organic cationic salt and an organic aluminum compound anion salt are uniformly mixed in an organic solvent,
It may be used as it is, or may be taken out once, purified and used later.

Preferred examples of the organic cationic dye portion (D-No), the quaternary ammonium salt portion (T-No), and the organic ammonium compound anion portion (A-No) that can be used in the present invention are shown below.

Preferred compounds that can be used in the present invention include salts obtained by optionally combining these organic cationic dye portions and / or quaternary ammonium salt portions and organic aluminum compound anion portions. However, the effects of the present invention are not limited to these compounds.

The organoaluminum compound used in the present invention can be synthesized by various methods. For example, a phenolic compound is reacted with trialkylaluminum, which is known to be inexpensive, to obtain dialkyl-phenoxyaluminum or monoalkyl-diphenoxyaluminum.
It can be synthesized by replacing with quaternary ammonium. Further, counterion exchange is carried out using the quaternary ammonium salt of the organic aluminum anion and the halogen salt of the cationic dye, whereby an organic aluminum compound anion salt of an organic cationic dye compound can be obtained.

In the image forming material of the present invention, it is preferable that the organoaluminum compound anion is present in excess with respect to the photobleachable dye. It is preferable that the organic aluminum compound anion is present in an amount of 1 to 10 mol per 1 mol of the dye,
More preferably, it is present in an amount of 1.1 to 5 mol.

The image forming material of the present invention can be prepared in various configurations depending on the purpose.

One preferred configuration is a layer containing fine droplets of a composition containing the photobleachable cationic dye of the present invention or an organoaluminum compound anion salt or a photobleachable nonionic dye and an organoaluminum compound anion salt. Is provided on the support. In this case, the droplet may be the core material of the microcapsule. There may be a binder in this layer.

When a multicolor image-forming material is obtained, for example, droplets or microcapsules containing photobleachable dyes of different hues may be mixed and used, and photobleachable dyes of different hues may be used in each layer. It is also possible to use a constitution of a multilayer recording material to be contained. At this time, if necessary, an intermediate layer between the layers may be provided, or a protective layer may be provided as the outermost layer of the material.

Hereinafter, the present invention will be described with reference to an image forming material having a layer containing a photobleachable dye in a binder on a support.

Although various methods can be used as a method for producing the image forming material of the present invention, a general method is to dissolve, emulsify or disperse the components of the photobleachable dye layer in an appropriate solvent. It comprises a step of preparing a liquid, applying the coating liquid to a support as described above, and drying to obtain an image forming material.

In the present invention, when the photobleachable dye is microencapsulated, it can be prepared by a method known in the art. For example, U.S. Pat.Nos. 2,800,457 and 2,8000,458, utilizing a coacervation of a hydrophilic wall forming material, U.S. Pat.No. 3,287,154, British Patent No. 990443, Japanese Patent Publication No. 38-19574, and Nos. 42-446 and 42-771, an interfacial polymerization method as disclosed in U.S. Pat.Nos. 3,418,250 and 3,660,304, and a method by precipitation of a polymer as disclosed in U.S. Pat.
6669, using isocyanate polyol wall material, US Pat. No. 3,914,511, using isocyanate wall material, US Pat.
U.S. Pat. No. 76,408982, a method using a urea-formaldehyde-based, urea formaldehyde-resorcinol-based wall-forming material, a method using a melamine-formaldehyde resin found in U.S. Pat. , Tokubo 36-9168
JP-A-51-9079, in-situ method by polymerization of monomers, British Patent Nos. 952807 and 96
Electrolytic dispersion cooling method found in 5074, U.S. Pat.
And the spray drying method shown in British Patent No. 930422. Although not limited thereto, it is preferable to form a polymer film as a microcapsule wall after emulsifying the core substance.

As for the method of forming the microcapsule wall, particularly when a microencapsulation method by polymerization of a reactant from the inside of an oil droplet is used, the effect is large. That is, it is possible to prepare a capsule in a short time to obtain an image-forming material having a uniform particle size and excellent raw storability.

For example, when polyurethane is used as the capsule wall material, a polyvalent isocyanate and, if necessary, a second substance (e.g., polyol,
(Polyamine) is mixed with an oily liquid to be encapsulated, emulsified and dispersed in water, and then heated to cause a polymer-forming reaction at the oil droplet interface to form microcapsule walls. At this time, an auxiliary solvent having a low boiling point and strong dissolving power can be used in the oily liquid.

In this case, the polyvalent isocyanate to be used and the polyol and polyamine to be reacted therewith are described in U.S. Pat. Nos. 3,281,383, 3,773,695, 3,793,268, and JP-B-48-108.
Nos. -40347 and 49-24159, JP-A-48-80191 and 48
No. 84086, which can also be used.

When forming droplets or microcapsules, a water-soluble polymer can be used, but the water-soluble polymer may be any of a water-soluble anionic polymer, a nonionic polymer, and an amphoteric polymer. As the anionic polymer, either a natural polymer or a synthetic polymer can be used.
-, -SO2- and the like. Specific anionic natural polymers include arabic gum, alginic acid, pectin and the like, and semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose, lignin sulfonic acid and the like.

In addition, as synthetic products, maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers and copolymers And carboxy-modified polyvinyl alcohol.

As the nonionic polymer, polyvinyl alcohol,
Examples include hydroxyethyl cellulose and methyl cellulose.

 Examples of the amphoteric compound include gelatin.

These water-soluble polymers are used as a 0.01 to 10% by weight aqueous solution. Droplet or microcapsule particle size
It is adjusted to 20 μm or less.

In the photobleachable dye layer of the present invention, a polymer binder can be optionally used. As a polymer binder,
Natural and synthetic polymers and polymer latexes known in the art can be used. For example, water-soluble polymers such as gelatin, polyvinyl alcohol, hydroxyethyl cellulose, polyvinyl pyrrolidone, casein, and starch. Polystyrene, polyvinyl formal, polyvinyl butyral, acrylic resin: for example, polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate and copolymers thereof, phenol resin,
Solvent-soluble polymers such as styrene-butadiene resin, ethylcellulose, epoxy resin, urethane resin, and the like, and polymer latexes thereof.

In the present invention, when a protective layer is provided, it is preferable to add a matting agent to the protective layer. Examples of the matting agent include silica, magnesium oxide, barium sulfate, strontium sulfate, inorganic compounds such as silver halide and polymethyl methacrylate, polyacrylonitrile, polymer particles such as polystyrene, carboxy starch, corn starch,
There are starch particles such as carboxynitrophenyl starch, and those having a particle diameter of 1 to 20 μm are preferable. Among these matting agents, polymethyl methacrylate particles and silica particles are particularly preferred. As silica particles, for example, FUJI
-SILOID AL-1, 65, manufactured by DEVISON CHEMICHAL LTD.
72, 79, 74, 404, 620, 308, 978, 161, 162, 244, 25
5, 266, 150, etc. are preferred. The addition amount of the matting agent is preferably 2-500 mg / m2, particularly preferably 5-100 mg / m2.
It is.

In the present invention, it is preferable to use a curing agent in combination with each layer of the recording material of the present invention such as a photobleachable dye layer, an intermediate layer and a protective layer.
As the hardener, for example, a `` gelatin hardener '' used in the production of photographic light-sensitive materials is useful, for example, formaldehyde, aldehyde compounds such as glutaraldehyde, and the reactivity described in U.S. Pat. Compounds having a halogen, compounds having a reactive ethylenically unsaturated bond described in U.S. Pat.No. 3,635,718 and others, aziridine-based compounds described in U.S. Pat.No.3017280 and others, described in U.S. Pat. Epoxy compounds, halogenocarboxaldehydes such as mucochloric acid, dihydroxy dioxane, dioxane such as dichloro dioxane or vinyl sulfones described in U.S. Patent No. 3642486 and U.S. Patent No. 3687707, U.S. Patent No. Vinyl sulfone precursors described in U.S. Patent No.
Ketovinyls described in JP-A-3640720 or chromium alum, zirconium sulfate, boric acid and the like can be used as an inorganic curing agent. Among these curing agents, particularly preferred compounds are 1,3,5-triacroyl-hexahydro-s-triazine, 1,2-bisvinylsulfonylmethane, 1,3-bis (vinylsulfonylmethyl) propanol-2, and bis ( α-vinylsulfonylacetamide) ethane, 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4,6-triethylenino-
Compounds such as s-triazine and boric acid. The addition amount is preferably 0.5 to 5% by weight based on the binder.

In addition, colloidal silica may be added to the protective layer to reduce the adhesiveness. As colloidal silica, for example, Nissan Chemical's Snowtex 20, Snowtex 30, Snowtex C, Snowtex O,
Snowtex N and the like are preferred. The addition amount is preferably 5-80% by weight based on the binder.

Further, a fluorescent whitening agent for increasing the whiteness of the image forming material of the present invention or a blue dye as a bluing agent may be added to the protective layer.

In the case of the multicolor image forming material of the present invention, for example, a multilayer image forming material having a plurality of layers containing photobleachable dyes of different hues is used, and an ultraviolet absorber is contained between each layer. A configuration in which an intermediate layer is provided may be adopted.

In this case, the intermediate layer mainly comprises a binder and an ultraviolet absorber, and may contain additives such as a curing agent and a polymer latex as needed.

Benzotriazole compounds as ultraviolet absorbers,
Known compounds such as a cinnamic acid ester compound, an aminoarylidenemalon nitrile compound, and a benzophenone compound can be used.

The ultraviolet absorber which can be used in the present invention can be emulsified and dispersed by an oil-in-water dispersion method or a polymer dispersion method and added to a desired layer, particularly, an intermediate layer. In the oil-in-water dispersion method, a high-boiling organic solvent having a boiling point of, for example, 175 ° C and a boiling point of, for example, 30 ° C
After dissolving in a single solution of a so-called auxiliary solvent having a temperature of 160 ° C. or lower or a mixture of both, it is finely dispersed in an aqueous medium such as water or an aqueous gelatin solution or aqueous polyvinyl alcohol solution in the presence of a surfactant. Examples of high boiling organic solvents are described in U.S. Pat. No. 2,322,027 and the like. Further, as specific examples of the high boiling point organic solvent and the auxiliary solvent, the same solvents as those used in the above-mentioned encapsulation can be preferably used. Further, the dispersion may be accompanied by a phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, Nudel washing, extrafiltration or the like before use for coating. No. 4,199,363.
No. 2, West German Patent Application (OLS) Nos. 2,541,274 and 2,54
No. 1,230, JP-A-49-74538, JP-A-51-59943, JP-A-54-3
2552 publications and Research Disclosure, Vol.148, August 1976
The latex dispersion method may be used with reference to Month, Item 14850, and the like.

As the ultraviolet absorber which can be preferably used in the present invention, there is an ultraviolet absorber having a structure hardly diffused into an adjacent layer, for example, a polymer or latex obtained by copolymerizing the ultraviolet absorber. Examples of such ultraviolet absorbers include European Patent No. 127,819 and JP-A-59-68731, JP-A-59-26733,
No. 59-23344, British Patent 2,118,315, JP-A-58-1119
No. 42, U.S. Pat.Nos. 4,307,184, 4,202,836, 4,202,
No. 834, No. 4,207253, No. 4,178,303, JP-A-47-560
No. etc. can be referred to.

These UV absorbers may be added to the intermediate layer,
Further, it may be added to a protective layer, a photobleachable dye layer, an antihalation layer and the like.

In the present invention, the dispersion or encapsulation of the photobleachable dye itself or an oil or a fixing agent in which the photobleachable dye is dissolved is preferably performed in a water-soluble polymer, but the water-soluble polymer which can be preferably used in the present invention is used. Preferred are compounds that dissolve in water at 25 ° C. in an amount of 5% by weight or more. Specifically, gelatin, gelatin derivatives, proteins such as albumin and casein, cellulose derivatives such as methylcellulose and carboxymethylcellulose, sodium alginate,
Saponification of sugar derivatives such as starches (including modified starch), gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolysate, carboxy-modified polyvinyl alcohol, polyacrylamide, vinyl acetate-polyacrylic acid copolymer And synthetic polymers such as polystyrene sulfonate. Among these, gelatin and polyvinyl alcohol are preferred.

In the present invention, as a binder for each layer of the image forming material such as a protective layer, a photobleachable dye layer and an intermediate layer, the above-mentioned water-soluble polymer and polystyrene, polyvinyl formal, polyvinyl butyral, acrylic resin: for example, polymethyl acrylate, polybutyl acrylate And solvent-soluble polymers such as polymethyl methacrylate, polybutyl methacrylate and copolymers thereof, phenol resins, styrene-butadiene resins, ethyl cellulose, epoxy resins, urethane resins, and the like, or polymer latexes thereof. Among these, gelatin and polyvinyl alcohol are preferred.

For each layer of the image forming material such as the photobleachable dye layer formed using the present invention, various surfactants are used for various purposes such as coating aids, antistatic, improving slipperiness, emulsifying and dispersing, and preventing adhesion. You may.

Examples of the surfactant include nonionic surfactants such as savonine, polyethylene oxide, polyethylene oxide derivatives such as alkyl ethers of polyethylene, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, and alkyl sulfates. Esters, N-acyl-N-alkyltaurines, sulfosuccinates, anionic surfactants such as sulfoalkylpolyoxyethylenalkylphenyl ethers, amphoteric surfactants such as alkylbetaines and alkylsulfobetaines, Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts can be used as needed.

Various additives can be added to the image forming material of the present invention, if necessary, including the additives described above. For example, typical examples of dyes, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, coating aids, curing agents, antistatic agents and slipperiness improvers for preventing irradiation and halation are Research Disclosure, Vol.176, December 1978, Ite
m 17643 and Vol. 187, November 1979, Item 18716.

To fix an image formed using the organoaluminum compound anion of the present invention, US Pat. No. 4,307,18
As described in No. 2, acetic acid, a fixing method using an acid such as stearic acid, or a photobleaching method using a colorless second bleaching dye described in EP 109,772. Can be used.

In the present invention, the image forming material of the present invention is prepared by dissolving the coating solution for the amount of photobleachable dye and the coating solution for each of the above-described layers in a solvent as necessary, coating the solution on a desired support, and drying. Is obtained. Examples of the solvent used in this case include water and alcohol: for example, methanol, ethanol, and n.
-Propanol, isopropanol, n-butanol,
sec-butanol, methyl cellosolve, 1-methoxy-
2-propanol; Halogen solvent: for example, methylene chloride, ethyl chloride; ketone: for example, acetone, cyclohexanone, methyl ethyl ketone; ester: for example, methyl cellosolve, ethyl acetate, methyl acetate;
Mixtures of more than one species are mentioned by way of example. Of these, water is particularly preferred.

To coat the coating solution for each layer on the support, a blade coater, a rod coater, a knife coater, a roll doctor coater, a comma coater, a reverse roll coater, a transfer roll coater, a gravure coater, a kiss roll coater, a curtain coater, an extender A lution coater or the like can be used. The application method is Research Disclosure, Vol. 200, December 1980, Ite
m Refer to section 20036 XV. An appropriate thickness of the recording layer is 0.1 μ to 50 μ.

The image forming material of the present invention can be used for various uses. For example, the image forming material of the present invention can be used for applications such as copiers, faxes, printers, labels, color proofs, overhead projectors, and second original drawings. Examples of suitable supports include paper, coated paper, laminated paper, synthetic paper and other supports and transparent films such as polyethylene terephthalate film, cellulose triacetate film, polyethylene film, polystyrene film, polycarbonate film, aluminum, zinc, and the like. Examples thereof include a plate made of metal such as copper, and a substrate obtained by subjecting the surface of the above-described support to various treatments such as surface treatment, undercoating, and metal vapor deposition.

As a support, Research Disclosure, Vol. 200, 1980
December, Item 20036 The support of section XVII can also be referred to. In addition, these supports may be provided with an antihalation layer on the front surface, and a slip layer, an anti-stick layer, an anti-curl layer, a pressure-sensitive adhesive layer, or the like, on the rear surface, if necessary.

Various exposure means can be used for the image forming material of the present invention. It goes without saying that commonly used light sources such as sunlight, tungsten lamps, mercury lamps, iodine lamps and other halogen lamps, xenon lamps, CRT light sources, plasma light sources, fluorescent tubes, light emitting diodes and the like can be used as light sources. Light source suitable for high illuminance, short time recording, such as strobe, flash, laser, LC
Exposure means combining a micro-shutter array using D (liquid crystal) or PLZT (lanthanum-doped lead zirconate titanate) and a linear or planar light source can also be used.

As the image recording method, various exposure methods such as contact exposure of an original such as a lith film, enlargement exposure of a slide or a liquid crystal image, and reflection exposure using reflected light of the original can be used. In the case of performing multicolor recording, image recording may be performed multiple times using light having different wavelengths. Light having different wavelengths can be obtained by changing the light source or the optical filter.

[Effect of the Invention] The image forming material of the present invention is a mono-sheet type using no inexpensive materials as a starting material, and a clear multicolor image can be easily obtained simply by image exposure.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

"Examples" Example 1 Photobleachable dye composition solutions S-1 to S-5 shown in Table 1
It was created.

One drop of each of the obtained photobleachable dye composition solutions S-1 to S-5 was dropped on a 100 μm polyethylene terephthalate film, and another polyethylene terephthalate film was further placed thereon to form a sample.

This sample is sandwiched between vacuum furnaces, and a step wedge (concentration step: 0.15, number of concentration steps: 0 to 15), jet light (Oak Co., 1KW) under vacuum through Fuji Step Guide P (Fuji Photo Film Co., Ltd.) Upon exposure to 50 counts, Samples S-2 and S-3 were light bleached in the form of a step wedge, and a clear positive image was obtained.

Jet light (1KW, made by Oak Co., Ltd.)
As a result of the count exposure, Sample S-5 was further bleached in the form of a step wedge, and a clear positive image was obtained.

It can be seen that the organic aluminum compound anion salt of the organic cationic dye of the present invention and the mixture of the nonionic dye and the organic aluminum compound anion salt are photo-bleached. Also, a mixture of an iodonium salt of an organic cationic dye and a tetrabutylammonium salt of an organic aluminum compound anion may form an organic aluminum compound anion complex of an organic cationic dye in a solution,
It can be seen that the complex has the same performance.

Monomer: trimethylolpropane triacrylate Dye compound (1), (iodonium salt of “D-7”) Dye compound (2) Organoaluminum compounds (1), (“A-1” and “T-
2 "salt) Organoaluminum compounds (2), (“A-1” and “D-
7 "salt) Example 2 Photobleachable dye assembling solution S-6 to S-9 shown in Table 2
It was created.

A sample was prepared in the same manner as in Example 1, and this sample was sandwiched between vacuum furnaces, and a step wedge (concentration step) was formed.
Exposure was performed 50 times using a jet light (1KW, manufactured by Oak Co., Ltd.) under a vacuum through a Fuji Step Guide P (manufactured by Fuji Photo Film Co., Ltd.) with a density of 0.15 and 0 to 15 steps.

In samples S-6 and S-7, the red color of the sample remained even after photobleaching. In each of S-8 and S-9, the exposed portion was bleached colorless.

Organic aluminum of the organic cation dye of the present invention It can be seen that in the case of the anion salt of the compound, the dye is sufficiently photobleached when the amount of the organoaluminum compound anio is at least 1.2 moles per mole of the dye.

Claims (10)

(57) [Claims] An image-forming material comprising a support and a layer containing an organic aluminum compound anion and a photobleachable dye provided on at least one surface of the support. 2. An image forming material according to claim 1, wherein said organoaluminum compound anion is represented by the following general formula (I). General formula (I) 3. The method according to claim 2, wherein said R1, R2, R3 and
An image-forming material, wherein at least one of R4 is a group represented by the general formula (II), (III) or (IV). General formula (II) -X-R5 General formula (III) General formula (IV) 4. The image forming material according to claim 1, wherein said photobleachable dye is a cationic dye. 5. The method according to claim 4, wherein said cationic dye is a dye selected from a cationic methine dye, a polymethine dye, a carbonium dye, a pyrylium compound, a quinone imine dye, a xanthene dye, an acridine dye and an azurenium dye. An image forming material comprising: 6. The method according to claim 4, wherein the cationic dye is a cationic cyanine / hemicyanine / styryl.
An image forming material, which is a dye selected from an azamethine dye, a triarylmethane dye, a pyrylium / thiapyrylium dye, an azine / thiazine / oxazine dye, and a rhodamine dye. 7. The image forming material according to claim 4, wherein said cationic dye is a dye having at least one indolenine skeleton or benzoselenazole skeleton. 8. An image forming material according to claim 1, wherein said organoaluminum compound anion is contained as a salt with a cation, and said photobleachable dye is a nonionic dye. . 9. The image forming material according to claim 8, wherein said nonionic dye is a dye selected from merocyanine dyes, coumarin dyes, xanthene dyes and thioxanthene dyes. 10. The image forming material according to claim 8, wherein said cation is a quaternary ammonium salt.