JPH08171212A - Picture recording method - Google Patents

Abstract

PURPOSE: To provide a novel picture recording method capable of forming a picture with a convenient process in the highly sensitive recording material with a silver halide as an optical sensor. CONSTITUTION: A recording material coated with a dyestuff decolored or discolored with at least a photosensitive silver halide, reducing agent, polymerizable compd., dyestuff decolored or discolored with a coordination compd. and coordination compd.is image-wise exposed to form a latent image, the material is heated simultaneously with or after the exposure to polymerize the polymerizable compd. at the part where the latent image exists, and the dyestuff at the unpolymerized part is decolored or discolored by the coordination compd. to obtain a picture. Otherwise, a recording material obtained by removing the coordination compd. or the dyestuff decolored or discolored by the coordination compd. from the material is used, the polymerizable compd. is polymerized, and then the material is brought into contact with the dyestuff decolored or discolored by the coordination compd. or the coordination compd. to decolor or discolor the dyestuff in the unpolymerized part.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording method.
More specifically, the present invention relates to a recording method in which a photosensitive silver halide is used as an optical sensor and a high molecular compound is generated in an imagewise manner by heating to erase or discolor the dye in the unpolymerized portion.

[0002]

2. Description of the Related Art A method for producing a polymer compound in an imagewise manner by utilizing the high photosensitivity of a photosensitive silver halide is described in detail in, for example, Japanese Examined Patent Publication No. 20741/1972. Was required, and the processing required a relatively long time. As a method of immobilizing coexisting color image-forming substances by generating a polymer compound corresponding to the exposed area, a system combining a vinyl compound and a photopolymerization initiator disclosed in JP-A-57-179836. It has been known. However, this method has remarkably low photosensitivity and requires a long exposure time as compared with a system using silver halide. Further, in recent years, as a method for obtaining an image by using a silver halide as an optical sensor to generate a polymer compound in an imagewise manner, it has been reported that a wet development process is not required. For example, JP-A-60-24
No. 9146, No. 61-6645, No. 61-73145
No. 61-75342, No. 61-100276, and the like, there are detailed descriptions, but most of the dye parts used in these methods are those which carry out color development-decolorization by utilizing an acid-base reaction. In addition to the above reports, most of the dyes developed an image-wise color. In the case of a dye utilizing the acid-base reaction, in the case of a system for developing a color, the developer (acid) is brought into contact with the developer at the time of development, and in the case of a system for decoloring, the developer added with the developer is deoxidized. The image is obtained by that. In such an image recording method, the stability of the photosensitive material before and after the image forming process such as non-imagewise coloring (thermal fog) and decoloration of the recorded image due to the structure of the dye suitable for use, and the stability of the formed image are improved. There was room for. Further, in the case of a color development reaction system, considering the reaction efficiency, it is necessary to add a large amount of a coloring material or the like in order to obtain a high image density, which is economically disadvantageous.

[0003]

The present invention is an improvement over these problems of the prior art. That is, the object of the present invention is to improve the storage stability of a recording material in dry rapid processing and the image stability after processing. Another object of the present invention is to provide an image recording method capable of achieving high image density. Still another object of the present invention is to provide a novel image recording method for obtaining an image by a simple method with a highly sensitive recording material using silver halide as an optical sensor.

[0004]

The object of the present invention is to coat a support with at least a photosensitive silver halide, a reducing agent, a polymerizable compound, a dye which discolors or discolors by a coordination compound, and a coordination compound. The provided recording material is imagewise exposed to form a latent image, and by heating at the same time as or after the exposure, the polymerizable compound in the portion where the latent image exists is polymerized, and the dye in the non-polymerized portion is coordinated with the coordination compound. This is achieved by an image recording method characterized by erasing or changing the color. A further object of the present invention is to use a recording material obtained by removing a coordination compound, or a dye that is discolored or discolored by the coordination compound, from the above-mentioned recording material, polymerizing a polymerizable compound, and then erasing or discoloring with the coordination compound. This can be achieved by an image recording method, which comprises contacting a dye that changes color or a coordination compound to decolor or change the color of the non-polymerized portion.

The recording material used in the present invention uses a photosensitive silver halide as an optical sensor, and a latent image nucleus of silver halide produced by exposure serves as a catalyst to cause an oxidation-reduction reaction between a silver salt and a reducing agent. A radical intermediate produced in the process is used as an initiator to cause a polymerization reaction to fix and stabilize the dye in the polymerized portion, and the dye in the non-polymerized portion is erased or discolored to obtain an image. In the present invention, depending on the type of photosensitive silver halide used, it is possible to obtain a dye image which is fixed and stabilized by a polymerization reaction corresponding to both exposed and unexposed areas. That is, when a normal negative type silver halide emulsion is used, a negative type image can be obtained with respect to the original image. On the other hand, in order to form a positive type image, US Pat.
No. 3, 3637778 and 3444927, the internal latent image type silver halide emulsions described in US Pat.
Mixtures of surface latent image type silver halide emulsions and internal latent image type silver halide emulsions as described in 96382 can be used.

The silver halide emulsion which can be used in the present invention is
It may be any of silver chloride, silver bromide, silver iodide, or silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. The halogen composition in the grains may be uniform. It may have a multiple structure having different compositions on the surface and inside (JP-A-57).
-154232, 58-108533, 59-
48755, 59-52237, U.S. Pat. No. 443.
3048 and EP100984). Further, tabular grains having a grain thickness of 0.5 μm or less, a grain size of at least 0.6 μm, and an average aspect ratio of 5 or more (US Pat.
4310, 4435499, and OLS3241
646A1 or the like) or a monodisperse emulsion having a substantially uniform grain size distribution (JP-A-57-178235 and 58-1).
No. 00846, No. 58-14829, WO83 / 02
338A1, EP64412A3, and 8337
7A1) may also be used in the present invention. Different crystal habit, halogen composition, particle size, particle size distribution, etc. 2
You may use together a silver halide of 1 or more types. The gradation can be adjusted by mixing two or more kinds of monodisperse emulsions having different grain sizes.

The grain size of silver halide used in the present invention is preferably from 0.001 μm to 10 μm, more preferably from 0.01 μm to 5 μm. These silver halide emulsions may be prepared by any of the acidic method, the neutral method and the ammonia method, and the reaction form of the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Any combination of A back mixing method, in which grains are formed in the presence of excess silver ions, or a controlled double jet method, in which pAg is kept constant, can also be adopted. Also, to accelerate particle growth,
The addition concentration, addition amount, or addition rate of the silver salt and halogen salt to be added may be increased (Japanese Patent Laid-Open No. 55-142).
No. 329, No. 55-158124, U.S. Pat. No. 3650.
757). An epitaxial type silver halide emulsion can also be used (JP-A-56-16124, U.S. Pat. No. 40).
94684).

In the present invention, when the silver halide is used alone without using the organic silver salt oxidizing agent, it is preferable to use silver chloroiodide or iodobromide capable of recognizing the X-ray pattern of the silver iodide crystal. Silver and silver chloroiodobromide. For example, a silver nitrate solution is added to a potassium bromide solution to prepare silver bromide grains, and further potassium iodide is added to obtain silver iodobromide having the above-mentioned properties.

In the step of forming silver halide grains used in the present invention, ammonia is used as a silver halide solvent, an organic thioether derivative described in JP-B-47-11386, or an organic thioether derivative described in JP-A-53-144319. A sulfur compound or the like can be used. In the process of grain formation or physical ripening, cadmium salt, zinc salt,
A lead salt, a thallium salt, etc. may coexist. Furthermore, for the purpose of improving high illumination failure and low illumination failure, iridium chloride (I
II), (IV), water-soluble iridium salts such as ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used.

Soluble salts may be removed from the silver halide emulsion after formation of a precipitate or after physical ripening, and therefore, the Nudel washing method or the precipitation method can be used. The silver halide emulsion may be used as it is without ripening, but it is usually chemically sensitized before use. The known chalcogen sensitizing method, reduction sensitizing method, noble metal sensitizing method and the like can be used singly or in combination for the emulsion for a conventional type light-sensitive material. These chemical sensitization methods can also be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Laid-open No. Sho 5).
8-126526, 58-215644).

The silver halide emulsion of the present invention may be either a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside the grain. When an internal latent image type emulsion is used, it is preferable to use a direct reversal emulsion together with a nucleating agent. Internal latent image type emulsions suitable for this purpose are disclosed in US Pat. Nos. 2,592,250 and 3,761,276.
And Japanese Examined Patent Publication No. 57-136641. A preferred nucleating agent to combine is US Pat.
No. 27552, No. 4245037, No. 4255511
No. 4266013, No. 4276364 and OL
S2635316. The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver. Preferably 10 mg to 3
g, more preferably 50 mg to 2 g.

In the present invention, a photosensitive silver halide may be used in combination with an organic silver salt, which is relatively stable against light, as an oxidizing agent. In this case, it is necessary that the photosensitive silver halide and the organic silver salt are in contact with each other or in a close distance. When heated to a temperature of 80 ° C., preferably 100 ° C. or higher, it is considered that the organometallic oxidant participates in the redox by using the latent image of silver halide as a catalyst. Examples of the organic compound that can be used to form such an organic silver salt oxidizing agent include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds. Is mentioned.

The silver salts of aliphatic carboxylic acids include behenic acid, stearic acid, oleic acid, lauric acid, capric acid, myristic acid, palmitic acid, maleic acid, fumaric acid, tartaric acid, furoic acid, linoleic acid and linolenic acid. ,
Typical examples are silver salts derived from adipic acid, sebacic acid, succinic acid, acetic acid, butyric acid, or camphoric acid. A silver salt derived from an aliphatic carboxylic acid having a halogen atom or a hydroxyl group-substituted product of these fatty acids or a thioether group can also be used. As the silver salt of aromatic carboxylic acid and other carboxyl group-containing compound,
Benzoic acid, 3,5-dihydroxybenzoic acid, o-, m-
Alternatively, p-methylbenzoic acid, 2,4-dichlorobenzoic acid, acetamidebenzoic acid, p-phenylbenzoic acid, gallic acid, tannic acid, phthalic acid, terephthalic acid, salicylic acid, phenylacetic acid, pyromellitic acid or 3-carboxymethyl A typical example is a silver salt derived from -4-methyl-4-thiazolin-2-thione.

The silver salt of a compound having a mercapto or thiocarbonyl group includes 3-mercapto-4-phenyl-1,2,4-triazole, 2-mercaptobenzimidazole, 2-mercapto-5-aminothiadiazole, 2- Mercaptobenzthiazole, S-alkyl thioglycolic acid (alkyl carbon number 12 to 2
2), dithiocarboxylic acids such as dithioacetic acid, thioamides such as thiostearoamide, 5-carboxy-1-methyl-2-phenyl-4-thiopyridine, mercaptotriazine, 2-mercaptobenzoxazole, mercaptooxadiazole or 3- Amino-5-benzylthio-1,2,4-triazole, etc. U.S. Pat. No. 4,123,2
Examples thereof include silver salts derived from the mercapto compound described in No. 74.

The silver salt of a compound having an imino group is
Benzotriazole or its derivative described in JP-B-44-30270 or 45-18416, for example, alkyl-substituted benzotriazoles such as benzotriazole and methylbenzotriazole, halogen-substituted benzotriazoles such as 5-chlorobenzotriazole, and butylcarbo Carboximidobenzotriazoles such as imidobenzotriazole, JP-A-58-11863
No. 9, nitrobenzotriazoles, JP-A-58-
Sulfobenzotriazole, carboxybenzotriazole or a salt thereof described in 118638, hydroxybenzotriazole, etc., and US Pat.
Representative examples include silver salts derived from 1,2,4-triazole described in No. 9, 1H-tetrazole, carbazole, saccharin, imidazole and derivatives thereof.

RD17029 (June 1978)
The metal salts other than silver salts such as those described in JP-A No. 1994-242, copper stearate and the like, and silver salts of carboxylic acids having an alkynyl group such as phenylpropiolic acid described in JP-A-60-113235 can also be used in the present invention. The above organic silver salt may be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is suitably 1 mg to 10 g / m ² .

The silver halide used in the present invention may be spectrally sensitized with dyes. Dyes used include methine dyes, cyanine dyes, merocyanine dyes,
It includes complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these dyes, any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be used. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nucleus of fused aromatic hydrocarbon ring, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus A nucleus, a quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms. In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazoline-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanin nucleus, A 5-6 membered heterocyclic nucleus, such as a thiobarbituric acid nucleus, can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used for the purpose of supersensitization. Along with the sensitizing dye, a dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion. For example, aminostyryl compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,743,510), Cadmium salt, azaindene compound, etc. may be contained. U.S. Pat. Nos. 3,615,613, 3,615,641, and 361.
The combinations described in Nos. 7295 and 3635721 are particularly useful.

Examples of the polymerizable compound that can be used in the present invention include addition-polymerizable monomers and their oligomers and polymers. As the addition-polymerizable monomer, a compound having at least one carbon-carbon unsaturated bond can be used. Examples of these include acrylic acid and its salts,
Acrylic acid esters, acrylamides, methacrylic acid and its salts, methacrylic acid esters, methacrylamides, maleic anhydride, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl Heterocycles and their derivatives. All of these compounds are useful in the present invention, but in the present invention, those having a boiling point of 80 ° C. or higher, which do not easily volatilize during heating because they are subjected to heat development processing, are preferable. Further, in order to increase the S / N ratio of the obtained color image, it is preferable to use a crosslinkable compound having an action of increasing the viscosity or the curing degree of the produced polymer compound in combination. The crosslinkable compound here is a so-called polyfunctional monomer having a plurality of vinyl groups or vinylidene groups in the molecule. Preferred examples of the polymerizable compound used in the present invention are shown below.
Acrylic acid, methacrylic acid, butyl acrylate, methoxyethyl acrylate, butyl methacrylate, acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-acryloylmorpholine, N
-Acryloyl piperidine, glycidyl acrylate,
2-ethylhexyl acrylate, acrylic acid anilide, methacrylic acid anilide, styrene, vinyltoluene, chlorostyrene, methoxystyrene, chloromethylstyrene, 1-vinyl-2-methylimidazole, 1-
Vinyl-2-undecylimidazole, 1-vinyl-2
-Undecyl imidazoline, N-vinyl pyrrolidone, N
-Vinylcarbazole, vinylbenzyl ether, vinylphenyl ether, methylene-bis-acrylamide, trimethylene-bis-acrylamide, hexamethylene-bis-acrylamide, N, N'-diacryloylpiperazine, m-phenylene-bis-acrylamide, p- Phenylene-bis-acrylamide, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate,
Polyethylene glycol diacrylate, bis (4-acryloxypolyethoxyphenyl) propane, 1,5-
Pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol acrylate, polopropylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, N-methylol acrylamide, diacetone acrylamide , Triethylene glycol dimethacrylate.

Condensation of acrylic acid or methacrylic acid with a polymer compound having a vinyl group or a vinylidene group, for example, a polymer compound having a hydroxyl group, an amino group, an epoxy group, a halogen atom or a sulfonyloxy group in its side chain. Objects and the like can also be used in the present invention. As will be described later, it is preferable that the dye or the coordination compound that is discolored or discolored by the coordination compound used in the present invention has a polymerizable vinyl group or vinylidene group in the molecule. The polymerizable compound may be the same molecule as the dye or coordination compound having these polymerizable functional groups. The polymerizable compound of the present invention can be used in an amount of 1 to 1200% by weight, preferably 10 to 5000% by weight, based on silver halide.

Examples of the reducing agent usable in the present invention include the compounds described in JP-B-47-20741, such as resorcins, m-aminophenols, m-phenylenediamines, 5-pyrazolones and alkylphenols.
Alkoxyphenols, naphthols, aminonaphthols, naphthalenediols, alkoxynaphthols, hydrazines, hydrazides and the like can be used. Among these compounds, hydrazides represented by the following general formula (1) can be particularly preferably used.

[0022]

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In the formula, R ₁ represents alkyl, alkenyl, aryl or aralkyl. R ₂ is a hydrogen atom, alkyl,
Represents aryl. R ₁ and R ₂ may be further substituted with the following substituents. That is, a halogen atom,
Alkyl (C1-20), alkenyl (C2-C2
22), aryl (having 6 to 24 carbon atoms), alkoxy (having 1 to 20 carbon atoms), aryloxy (having 6 to 24 carbon atoms), alkylthio (having 1 to 20 carbon atoms), arylthio (having 6 to 24 carbon atoms), acyl ( 2 to 22 carbon atoms, sulfonyl (1 to 20 carbon atoms), carbamoyl (2 to 2 carbon atoms)
2), sulfamoyl (carbon number 1 to 20), carbonamide (carbon number 2 to 22), sulfonamide (carbon number 1 to 1)
20). A and B represent a hydrogen atom, or acyl or sulfonyl, and at least one of A and B represents a hydrogen atom. G represents carbonyl, sulfonyl and dicarbonyl. Specific examples of preferable reducing agents in the present invention are shown below, but the present invention is not limited thereto.

[0024]

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[0025]

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Two or more kinds of these reducing agents may be used in combination, if necessary. Further, the reducing agent may be used in combination with a conventional photographic reducing agent such as hydroquinone, catechol, p-substituted aminophenols, p-phenylenediamines, 3-pyrazolidones. The amount of reducing agent added can vary widely,
Generally, it is 0.1 to 1500 mol%, preferably 10 to 300 mol% with respect to the silver salt. Furthermore, compounds in which a vinyl group or a vinylidene group is condensed to the mother nucleus of these reducing agents, such as m-N, N-di (acryloyloxyethyl) aminophenol and p-acryloyloxyethoxyphenol, are polymerizable with the reducing agent. A compound can also be used. Similar to the above-mentioned crosslinkable compound, those having these polymerizable groups are more preferable from the viewpoint of increasing the curing degree of the produced polymer compound, and thus the stability of the dye in the polymerized portion.

In the present invention, it is preferable that at least one of a dye and a coordination compound which are decolored or discolored by the coordination compound is contained in the polymerization part for imagewise development polymerization and is stabilized by the polymerization. The dye that can be used in the present invention is characterized by being decolored or discolored by the action of a coordination compound. The decolorization or the mechanism of decolorization mainly occurs when the coordination compound deprives the metal of the dye that develops color in the presence of the metal ion. Dyes that develop color in the presence of metal ions include dyes that are ligands that are colored by coordination with metal ions (so-called chelate dyes), as well as dyes that directly form themselves. Is a dye-donor compound (leuco dye) that does not participate in
A dye or the like that develops a color by interaction with a specific compound (developing agent) containing a metal ion can be used.

The mother nucleus of the dye that can be used in the present invention is
US Pat. No. 5,135,842, EP Patent No. 060528
In addition to polymethine dyes described in No. 6, azo dyes,
Any known dye such as various cyanine dyes and xanthene dyes can be used. Typical examples of chelate dyes are indicators used for chelate titration in the field of analytical chemistry, chelate dyes used for colorimetric determination, and the like. Hen, Showa 5
0 years, especially p. 1526), Experimental Chemistry Guidebook (Maruzen, published in 1984, especially p.738), and Dye Handbook (edited by the Society of Synthetic Organic Chemistry, published in 1945). And derivatives thereof are useful in the present invention. On the other hand, dyes that utilize color development due to the interaction between a dye-donor compound (leuco dye = color-developing agent) that does not directly participate in coordination and a specific compound containing a metal ion (developing agent) include pressure-sensitive paper and thermosensitive paper. A combination of a color-developing agent and a color-developing agent used for paper or the like is useful. Compounds having a partial structure such as lactone, lactam, and spiropyran are useful as the color former, and include triarylmethane compounds, diphenylmethane compounds, xanthene compounds, thiazine compounds, and spiropyran compounds. In particular, many triarylmethane compounds and xanthene compounds give little fog and give a high color density, and are very useful in the present invention. Examples of color formers are crystal violet lactone, 3-diethylamino-6-chloro-7.
-(Β-Ethoxyethylamino) fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3
-Dimethylamino-6-chloro-7-anilinofluorane, 3-cyclohexylmethylamino-6-methyl-7
-Anilinofluorane, 3-diethylamino-7-o-
Chloroanilinofluorane and the like are included. Detailed examples of the color former are disclosed in JP-A-55-27253 and JP-A-62-2094.
No. 36, No. 62-288827, No. 62-28882.
No. 8, No. 63-53542, No. 63-112188.
No. 63-112190, No. 63-113446
No. 63-129338, No. 63-199286.
No. 63-251278 and 63-2251279.
No. 63-2251280, No. 64-25148.
And Japanese Patent Application Laid-Open No. 2-45189. Two
You may mix and use 1 or more types of color formers. A metal salt of an organic acid is useful as the developer containing a metal ion. Examples of organic acids include phthalic acid, phthalic anhydride, maleic acid,
Benzoic acid (including oxybenzoic acid) gallic acid, o- and p-toluic acid are included. Oxybenzoic acid and its derivatives, especially salicylic acid and its derivatives are preferred. Examples of salicylic acid derivatives include 3-t-butylsalicylic acid,
3,5-t-dibutylsalicylic acid, 5-α-methylbenzylsalicylic acid, 3,5-bis (α-methylbenzyl)
Examples thereof include salicylic acid and 3-t-octylsalicylic acid. As examples of metal ions, zinc ions, lead ions, aluminum ions, magnesium ions, and nickel ions are useful. Zinc ions and aluminum ions are excellent in terms of color development performance, storability of color image, and sensible material. For a detailed example of the color developing agent, see Japanese Patent Publication No. 52-13.
27, JP-A-3-138191, U.S. Pat. No. 386.
No. 4146, No. 4046941 and the like. You may mix and use 2 or more types of color developers. Further, when these dyes are contained in the polymerized portion that undergoes image-wise development polymerization and the dyes are stabilized by polymerization, those having a small polymerization inhibitory property are more preferable as the properties of the dyes. Generally, dyes that act as inhibitors of polymerization reactions have the ability to inhibit radicals,
Examples include quinoid, azo, and azomethine dyes. However, since the degree of polymerization inhibition varies depending on individual dye molecules, it is desirable to conduct a polymerization inhibition test in advance when using the present invention. Further, when these dyes are contained in the polymerized portion that undergoes image-wise development polymerization and the dyes are stabilized by polymerization, these dyes have a form in which a radically polymerizable site such as a vinyl group or vinylidene group is bonded in the molecule. Are more preferred.

Specific examples of dyes that are decolorized or discolored by the coordination compound useful in the present invention are shown below, but the present invention is not limited thereto.

[0030]

[Chemical 4]

[0031]

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[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

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[0035]

[Chemical 9]

[0036]

[Chemical 10]

[0037]

[Chemical 11]

The dye which is decolored or discolored by the coordination compound used in the present invention is 0.5 with respect to the polymerizable compound.
It is preferably used in the range of 2 to 500% by weight, 2
It is more preferable to use in the range of to 200% by weight. When the dye used in the present invention is a color former and a color developer, the color former is 0.5 to 500 relative to the polymerizable compound.
It is preferable to use it in the range of 2 to 200% by weight.
It is more preferably used in the range of 50% by weight, and the developer is preferably used in the range of 50 to 1000% by weight, more preferably 100 to 1000% by weight based on the color former.

As the coordination compound which can be used in the present invention, any chemical compound which is generally known in organic chemistry and which can form a coordination bond can be used.
Useful organic coordination compounds include amines (especially polyamines), nitrogen-containing heteroaromatic rings (especially nitrogen-containing heteroaromatic rings having a carboxylic acid-containing substituent), amino alcohols, aminocarboxylic acids (especially Aminopolycarboxylic acids, polyaminopolycarboxylic acids), 1,2- and 1,3-dicarbonyl compounds, oximes, Schiff bases, polyethers, polyalcohols and the like are useful. Detailed examples of coordination compounds, Experimental Chemistry Course 4th Edition
Volume 17 (edited by The Chemical Society of Japan, Maruzen, 1991), Chelate Chemistry Vol. 1-6 (Nankodo, 1975-52), etc. (A part is described as a coordination compound with a metal.) Two or more coordination compounds may be mixed and used. All of these compounds are useful in the present invention, but in the present invention, those having a boiling point of 80 ° C. or higher, which do not easily volatilize during heating because they are subjected to heat development processing, are preferable. Similar to the above-mentioned dyes, these coordination compounds preferably have a form in which a radically polymerizable site such as a vinyl group or a vinylidene group is bonded in the molecule, from the viewpoint of stabilizing the dye in the polymerized part. Furthermore, since these coordination compounds must be included in the photosensitive material separately from the decolorizable dye until the development processing, they must be dispersed in a different layer when the photosensitive material is designed. It is more preferable to add it by a method or to make it into a precursor. The precursor here is one that causes a chemical reaction during heat development to release a coordination compound. As the precursor, intramolecular nucleophilic substitution reaction, Rossen rearrangement,
A compound that decomposes by a reaction such as Beckmann rearrangement to release an amine and that releases a coordination compound by causing some reaction by heating is preferably used. Furthermore, when these coordination compounds are contained in the polymerized portion that undergoes image-wise development polymerization and the coordination compounds are stabilized by the polymerization, those having small polymerization inhibitory properties are more preferable as the properties of the coordination compounds. In addition, when these coordination compounds are contained in the polymerized part that undergoes image-wise development polymerization and the coordination compounds are stabilized by polymerization, these coordination compounds can undergo radical polymerization such as vinyl groups and vinylidene groups in the molecule. It is more preferable that the site is bound.

Specific examples of the coordination compound useful in the present invention are shown below, but the present invention is not limited thereto.

[0041]

[Chemical 12]

[0042]

[Chemical 13]

[0043]

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[0044]

[Chemical 15]

The coordination compound used in the present invention is preferably used in the range of 10 to 10000 mol%, more preferably 50 to 5000 mol% based on the dye.

In the present invention, various accelerators can be used to accelerate the reaction between the silver salt and the reducing agent. As the accelerator, there is a compound that makes the reaction system basic to accelerate development, and this includes a base or a base precursor. Various bases or base precursors are known. The base precursor referred to here is one that releases a base component upon heating, and an organic base that is sterically bulky is preferable. Examples of preferable bases include aliphatic amines (trialkylamines, hydroxylamines,
Aliphatic polyamines), aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxyalkyl-substituted aromatic amines and bis [p- (dialkylamino) phenyl] methanes), heterocyclic amines, Examples include substituted amidines, cyclic amidines, polysubstituted guanidines, cyclic guanidines, and polysubstituted bisguanidines, with pKa of 8 or more being preferable, and pKa of 10 or more being more preferable.

When the base is contained in the light-sensitive material, it is preferably added in the form of a precursor. As the base precursor, a salt of an organic acid and a base that is decarboxylated and decomposes by heating, a compound that decomposes by a reaction such as intramolecular nucleophilic substitution reaction, Rossen rearrangement, Beckmann rearrangement, etc. to release amines, etc. Those that cause a reaction to release a base are preferably used. Preferred base precursors are salts of trichloroacetic acid described in British Patent No. 998,949, salts of α-sulfonylacetic acid described in U.S. Pat. No. 4,060,420, JP-A-59-180537.
Salts of propiolic acids described in U.S. Pat.
JP-A-59-168440 utilizing the 2-carboxycarboxamide derivative described in JP-A-496 and the Rossen rearrangement.
And the aldoxime carbamates described in JP-A-59-157637, which produces a nitrile by heating. Others, British Patent No. 998945 and US Patent No. 32208
46, JP-A-50-22625, British Patent No. 207.
The base precursor described in 9480 is also useful. Specific examples of the base precursor particularly useful in the present invention are shown below.

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[0049]

[Chemical 17]

These bases can be used alone or in combination of several kinds. Further, these bases or base precursors can be used in a wide range. The useful range is 50% by weight of the dry film of the light-sensitive material converted to weight.
Below, more preferably 0.01 to 40% by weight
Range.

In the present invention, the reducing agent, the polymerizable compound, the decolorizable dye (color-changing dye) and the coordination compound can be introduced into the image recording material by various methods. For example, a solution dissolved in water or a hydrophilic organic solvent can be directly coated on a support together with a binder if necessary. Further, it can be incorporated into the layer of the light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.),
Phosphate ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.), citrate ester (eg acetyl citrate tributyl), benzoate ester (octyl benzoate), alkylamide (eg diethyl lauryl amide) A high boiling point organic solvent such as a fatty acid ester (eg, dibutoxyethyl succinate, dioctyl azelate), trimesic acid ester (eg, tributyl trimesate), or a boiling point of about 30 to 100
After being dissolved in an organic solvent at 0 ° C., for example, lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate methyl cellosolobate acetate, cyclohexanone, etc., Dispersed in hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used. In addition, Japanese Patent Publication No. 51-39853
The dispersion method using a polymer described in JP-A-51-59943 can also be used. Further, various surfactants can be used when dispersed in the hydrophilic colloid.

Further, these components may be encapsulated and coated on a support. This method is particularly preferable for the purpose of obtaining high image quality. It is desirable to use a solvent together when encapsulating. As the solvent, phenylalkanes, chlorinated paraffins and the like are preferable in addition to the above-mentioned organic solvents. At that time, the polymerizable compound is contained in the capsule in an amount of 5 to 9
5% by weight, and the decolorizable dye (discoloring dye) is preferably contained in an amount of about 0.1 to 15% by weight. As the capsule wall, those utilizing coacervation of gelatin, polyurea, polyureethane, polyester, thermosetting polymer or a mixture thereof are preferable. In particular, when a method by polymer precipitation or an encapsulation method by polymerization of a reactant from an oily interior is used, a capsule having a uniform particle size, a dense wall and excellent storage stability can be obtained. A specific example of encapsulation is US Pat. No. 3,726,804.
No. 3,796,669. The particle size of the capsules is preferably 80 μm or less, particularly 20 μm or less from the viewpoint of handleability during storage. In addition, 0.1 μm or more is desirable from the viewpoint of ease of pressurization. That is, the capsule does not change substantially under pressure, about 10 kg / cm ² or less,
It is desirable that about 50% or more of the capsules are destroyed at about kg / cm ² . The capsule is coated on the support so that the decolorizable dye (color-changing dye) is about 0.1 g to 5 g / m ² .

The binder used in the present invention may be contained alone or in combination. As the binder, a hydrophilic one can be mainly used. As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical. For example, proteins such as gelatin, gelatin derivatives, and cellulose derivatives, natural products such as other saccharides such as starch arabic gum, polyvinylpyrrolidone, and acrylamide. Includes synthetic polymeric materials such as water soluble polyvinyl compounds such as polymers. Other synthetic polymeric materials are vinyl compounds in dispersion form, especially in the form of latexes, which increase the dimensional stability of photographic materials.

The support used in the photosensitive material of the present invention can withstand the processing temperature. As a general support, not only glass, paper, metal and its analogs are used, but also acetyl cellulose film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film and those related thereto. Includes film or resin material. A paper support laminated with a polymer such as polyethylene can also be used. US Patent 36
The polyesters described in Nos. 34089 and 3725070 are preferably used. The image recording material of the present invention is a protective layer, an anti-curl layer, a fluorescent whitening agent, an anti-fading agent, a halation or anti-irradiation dye, a pigment, if necessary.
It may contain a water releasing agent, a thermal polymerization inhibitor, a surfactant, a thermal solvent and the like.

The image recording material according to the present invention comprises a reducing agent, a polymerizable compound, a decolorizable dye (color-changing dye),
It is possible to take various forms depending on the method of introducing the coordination compound and the silver halide emulsion, the layer constitution upon coating, and the like. When forming a monosheet recording material, it is necessary to introduce the decolorizable dye (color-changing dye) and the coordination compound in separate forms. As a method of separation, for example,
Add a decolorizable dye (color-changing dye) and a coordination compound to another layer in a multi-layer structure, or a coordination compound precursor is solid-dispersed and incorporated in a form that does not react with the dye until heat development, or further A method in which a decolorizable dye (color-changing dye) or a coordination compound precursor is included in microcapsules is possible. When using microcapsules, it is possible to bring the coordination compound into contact with the dye after the development polymerization is completed. When forming a two-sheet recording material, the coordination compound and the erasable dye (discoloring dye) may be incorporated in separate sheets, so each component uses one of the above-mentioned introduction methods. It is possible to do it.

Various exposure means can be used in the present invention. The latent image is obtained by imagewise exposure of radiation including visible light. Generally, a commonly used light source such as sunlight, strobe, flash, tungsten lamp, mercury lamp, iodine lamp, or other halogen lamp, xenon lamp, laser beam, CRT light source, plasma light source, fluorescent lamp, light emitting diode, etc. is used as a light source. be able to. Further, it is also possible to use an exposure means in which a micro-shutter array utilizing LCD (liquid crystal) or PLZT (lanthanum-doped titanium zirconate) and a linear light source or a flat light source are combined. The type of light source and the amount of exposure can be selected according to the sensitivity wavelength and sensitivity due to dye sensitization of silver halide. The original image used in the present invention may be a monochrome image or a color image.
The original image may be not only a line image such as a drawing but also a photographic image having gradation. It is also possible to shoot a person image and a landscape image using a camera. The printing from the original image may be carried out by superposing it on the original image, followed by contact baking, reflection baking, or stretching baking. It is also possible to directly output an image taken by a video camera or the like or image information sent from a television station to a CRT or FOT, form an image of this image on a photosensitive material by contact or a lens, and print it. .

Further, LEDs which have made great progress in recent years
(Light emitting diodes) are being used as exposure means in various devices. It is difficult to make this LED that effectively emits blue light. In this case, in order to reproduce a color image, three types of LEDs that emit green light, red light, and infrared light are used, and the emulsion portions that are exposed to these lights are yellow, magenta, and cyan decolorizable dyes ( It is good to include a color-changing dye. Other combinations other than this are possible according to need. In addition to the method of directly contacting or projecting the above original drawing, the original drawing irradiated by the light source is received by a light receiving element such as a photoelectric tube or CCD
After reading the image information into a memory such as a reading computer and processing this information as necessary, so-called image processing, playing this image information on a CRT and using it as an image-like light source, or based on the processed information. Then, there is also a method of directly exposing the three kinds of LEDs to emit light.

In the present invention, as a heating method at the same time as or after the imagewise exposure, a conventionally known method can be used. For example, the photosensitive material may be brought into direct contact with a hot plate such as a hot plate or a drum, or may be conveyed using a heat roller. Further, it is also possible to use air heated to a high temperature, high frequency heating or heating with a laser beam. Depending on the photosensitive material, it can also be heated by using an infrared heater. Further, a method of heating by utilizing overcurrent generated by electromagnetic induction can be applied. Further, a liquid inert to the light-sensitive material, for example, a fluorinated alkyl liquid may be heated in a heated bath. Further, the above-mentioned heating means may be heated by providing a heat source to the photosensitive material. For example, a layer of conductive particles such as carbon black or graphite may be provided on the photosensitive material and Joule heat generated when electricity is applied may be used. The heating temperature at this time is generally 80 to 20.
The temperature is 0 ° C, preferably 100 to 160 ° C. Various patterns can be applied as a pattern for heating the photosensitive material. The method of heating at a constant temperature is most common, but multi-step heating-for example, a method of gradually lowering the temperature after heating at high temperature for a short time-is effective depending on the characteristics of the photosensitive material.
The heating time in this case is generally 5 seconds to 5 minutes, preferably 5 seconds.
Seconds to 1 minute. When the photosensitive material is easily affected by air during heating, it is effective to degas the surroundings of the heating portion or replace it with an inert gas. The surface of the light-sensitive material may be brought into direct contact with the heated portion or may be exposed to air. When developing with the surface of the photosensitive material on the air side, it is effective to prevent evaporation of moisture and volatile components from the photosensitive material and to attach a cover for the purpose of keeping heat.

[0059]

EXAMPLES The photosensitive recording material of the present invention will be specifically described below with reference to examples. Example 1 5 g of 2-ethylhexyl acrylate, 2 g of methylenebisacrylamide, 1.5 g of silver behenate (3.3 mmo)
l), reducing agent (R-1) 0.81 g (5.9 mmol), color former (H-1) 0.74 g (1.2 mmol), color developer (K
-3) A mixture of 1.9 g (5 mmol) and 3 ml of methanol was dispersed with a high speed shearing stirrer for 10 minutes at 10,000 rpm. The above dispersion was applied onto a polyethylene terephthalate film in a wet film thickness of 40 μm and dried.
Then 1.7 g (10 mmol) of the coordination compound (L-17),
2-ethylhexyl acrylate 3 g, 1% sodium dodecylbenzenesulfonate aqueous solution 2 ml, methanol 1
A mixture of 1 ml was applied and dried to prepare a light-sensitive material. The coated silver amount was about 0.3 g in terms of silver. The above light-sensitive material was imagewise exposed at 2000 lux for 5 seconds using a tungsten bulb. Then, when it was heated for 15 seconds on a hot plate heated to 110 ° C., a clear magenta image corresponding to the exposed portion was obtained.

Example 2 (Preparation of Solid Dispersion of Base Precursor) In a 300 ml dispersion container, 110 g of a 5.4% aqueous solution of gelatin,
80 g of base precursor (B-1) and a diameter of 0.5 to
200 ml of 0.75 mm glass beads were added, and dispersed using a Dynomill at 3000 rpm for 30 minutes. The pH was adjusted to 6.5 with 1M sulfuric acid to obtain a solid dispersion of the base precursor. The particle size of the base precursor (B-1) is
It was 1.0 μm or less. (Preparation of Photosensitive Composition) Silver iodobromide (iodine / bromine = 1
1) 10% by weight, gelatin 7% by weight 2 g, silver halide emulsion 2 g, pentaerythritol tetraacrylate 5 g, reducing agent (R-2) 0.3 g (0.95 mmol),
2.5 g (14.6 mmol) of the coordination compound (L-17), 9 g of the above base precursor (B-1) solid dispersion, 0.3 g of sorbitol, 1 ml of 5% sodium dodecylbenzenesulfonate aqueous solution, and 4 ml of ethyl acetate. The mixture was dispersed using a high speed shear stirrer for 10 minutes at 10,000 rpm. (Preparation of recording material) 1.0 g of color former (H-2) (2.1
mmol) and 3.0 g (7.9 mmol) of the color developer (K-3) are dissolved in 5 ml of ethyl acetate, and this is mixed with 2 g of 10% polyvinyl alcohol aqueous solution and 0.5 ml of 5% sodium dodecylbenzenesulfonate aqueous solution, Dispersion was performed at 10,000 rpm for 5 minutes using a high speed shear stirrer. This was applied onto a polyethylene terephthalate film with a wet film thickness of 30 μm and dried. Next, the photosensitive composition prepared above was applied in a wet film thickness of 40 μm and dried to prepare an image recording material. (Image exposure and recording) 2000 lux using a halogen lamp through the step wedge in the above-mentioned light-sensitive material,
After exposure for 5 seconds, the film was passed through a heat roller heated to 120 ° C., and a black image corresponding to the exposure was obtained.

Example 3 10 g of benzotriazole silver emulsion described in JP-A-61-73145, silver iodobromide emulsion (iodine / bromine = 1/1)
3 g, base precursor described in Example 2 (B-1)
Solid dispersion 18 g, pentaerythritol tetraacrylate 25 g, N-butyl acrylamide 10 g, reducing agent (R-7) 0.4 g (1.2 mmol), dye (D-
3) 3 g, cyclohexanone 8 g, sorbitol 4 g,
5% sodium dodecylbenzenesulfonate aqueous solution 10
A mixture of 10 ml of water and 10 ml of water was dispersed for 15 minutes at 8000 rpm using a high speed shear stirrer. The obtained dispersion was applied on a polyethylene film so that the wet film thickness was 40 μm, and dried. Then the coordination compound (L-
3) 5 g of methanol was mixed with 5 ml of methanol and 10 ml of a 5% sodium dodecylbenzenesulfonate aqueous solution, dispersed, coated and dried to prepare a recording material. After exposing the above recording material to 2000 lux for 10 seconds using a tungsten lamp, 1
When heated for 15 seconds on a hot plate heated to 20 ° C., a red image corresponding to the exposed portion was obtained.

Example 4 (Preparation of Microcapsules Containing Coordination Compound) Isobutylene-maleic anhydride copolymer was treated with alkali to mix 11.7 g of ring-opened 18.6% aqueous solution with 54 g of pectin 2.9 g aqueous solution. Then, the pH was adjusted to 4 with 10% sulfuric acid to prepare a protective colloid aqueous solution. On the other hand, the coordination compound (L-
6) 11.2 g (50 mmol), 10 g of tricresyl phosphate, and 40 g of ethyl acetate were mixed and dissolved. This solution was added to the above protective colloid aqueous solution and emulsified with a homogenizer to obtain oil droplets having an average particle size of 6μ. To 70 g of this emulsion, 8.3 g of 40% aqueous solution of urea, 2.8 g of 11% aqueous solution of resorcin, 8.6 g of 37% aqueous solution of formalin and 2.7 g of 8.8% aqueous solution of ammonium sulfate were added and mixed well, The heating and stirring were continued at 60 ° C. for 2 hours. After cooling, the pH was adjusted to 7 using a 10% aqueous solution of sodium hydroxide, and then 31% of sodium bisulfite was added.
An aqueous solution (3.6 g) was added to prepare a microcapsule dispersion containing a coordination compound (L-6).

(Preparation of recording material) JP-A-67-1314
No. 5, 10 g of benzotriazole silver emulsion, 2 g of silver iodobromide emulsion (iodine / bromine = 1/1), 15 g of solid dispersion of the base precursor (B-1) described in Example 2,
Pentaerythritol tetraacrylate 30 g, N-
Butylacrylamide 5 g, reducing agent (R-11) 0.4
7 g (1.5 mmol), color former (H-3) 5.5 g (1
0.4 mmol), developer (K-10) 8 g, ethyl acetate 1
A mixture of 5 ml, 5 g of sorbitol, 8 ml of a 5% sodium dodecylbenzene sulfonate aqueous solution and 8 ml of water was dispersed at 8000 rpm for 15 minutes using a high speed shearing stirrer. The obtained dispersion was applied on a polyethylene film so that the wet film thickness was 40 μm, and dried. Next, the coordination compound microcapsule dispersion prepared above was applied to a wet film thickness of 30 μm and dried. (Exposure and recording of image) The obtained light-sensitive material was imagewise exposed at 2000 lux for 10 seconds using a tungsten lamp, and then heated for 20 seconds on a hot plate heated to 100 ° C. Then, the light-sensitive material was laminated with a polyethylene film and then passed through a pressure roller, whereby a yellow image corresponding to the exposed portion was obtained.

Example 5 (Preparation of Photosensitive Dye Sheet) Silver iodobromide (element / bromine =
1/1) 10% by weight, gelatin 7% by weight silver halide emulsion 2 g, pentaerythritol tetraacrylate 5 g, reducing agent (R-2) 0.3 g (0.95 mmo
l), 1.24 g (2.5 mmol) of color former (H-4), 1.9 g (5 mmol) of color developer (K-3), and 8 g of solid dispersion of the base precursor (B-1) of Example 2. , Sorbitol 0.3 g, 5% sodium dodecylbenzenesulfonate aqueous solution 2 ml, 15% polyvinyl alcohol aqueous solution 5 ml,
And a mixture of 4 ml of ethyl acetate with a high speed shear stirrer.
Dispersion was performed at 10,000 rpm for 0 minutes. The obtained dispersion was applied onto a polyethylene terephthalate film with a wet film thickness of 40 m and dried. (Preparation of Coordination Compound Sheet) Coordination Compound (L-2) 1.
4 g (5 mmol) was dissolved in 5 ml of methanol, then mixed with 1 ml of 5% sodium dodecylbenzenesulfonate aqueous solution, coated on a polyethylene elephthalate film, and dried. (Exposure and recording of image) The above-mentioned photosensitive dye sheet was exposed to 2000 lux for 10 seconds using a halogen lamp through a step wedge, and then heated for 15 seconds on a hot plate heated to 120 ° C. Then, the heat-treated photosensitive dye sheet was superposed on the above-mentioned coordination compound sheet, passed through a heat roller heated to 100 ° C., and then the coordination compound sheet was peeled off to obtain a black image corresponding to the exposed portion. It was

Comparative Example A comparative sample A was prepared and an image was obtained in exactly the same manner as in Example 1 described in JP-A-61-1100466. The comparative sample A and the image sample prepared in Example 5 of the present invention were left for one week at the window exposed to the direct sunlight, and then the image density was measured again. In the comparative sample A, a remarkable decrease in color image density was observed. However, in the sample of Example 5 of the present invention, almost no decrease in concentration was observed.

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[Procedure amendment]

[Submission date] January 30, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

Condensation of acrylic acid or methacrylic acid with a polymer compound having a vinyl group or a vinylidene group, for example, a polymer compound having a hydroxyl group, an amino group, an epoxy group, a halogen atom or a sulfonyloxy group in its side chain. Objects and the like can also be used in the present invention. As will be described later, it is preferable that the dye or the coordination compound that is discolored or discolored by the coordination compound used in the present invention has a polymerizable vinyl group or vinylidene group in the molecule. The polymerizable compound may be the same molecule as the dye or coordination compound having these polymerizable functional groups. The polymerizable compound of the present invention is contained in an amount of 1 to 12000% by weight, preferably 10 to 5000, based on silver halide.
% By weight can be used.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

[0024]

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 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideki Maeda 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (2)

[Claims] 1. A recording material in which at least a photosensitive silver halide, a reducing agent, a polymerizable compound, a dye which discolors or discolors by a coordination compound, and a coordination compound are coated on a support by imagewise exposure. Characterized by forming a latent image and polymerizing the polymerizable compound in the portion where the latent image exists by heating at the same time as exposure or after that, and discoloring or discoloring the dye in the non-polymerized portion by the coordination compound Image recording method. 2. A latent image is formed by imagewise exposing a recording material having a support coated with at least a photosensitive silver halide, a reducing agent, a polymerizable compound, and a dye that is discolored or discolored by a coordination compound. Then, simultaneously with exposure, or after that, by heating to polymerize the polymerizable compound in the portion where the latent image exists, then, by contacting the coordination compound, to discolor or discolor the dye in the non-polymerized portion, Alternatively, a latent image is formed by imagewise exposing a recording material in which at least a photosensitive silver halide, a reducing agent, a polymerizable compound, and a coordination compound are coated on a support to form a latent image, and heating is performed simultaneously with or after the exposure. Is characterized by polymerizing the polymerizable compound in the area where the latent image is present, and then contacting the dye that is discolored or discolored by the coordination compound to discolor or discolor the dye in the non-polymerized area. Image recording method.