JPH0222938B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method and photographic material for converting electrical signals into light and recording color images on a photographic material.

Various methods are known for converting electrical signals corresponding to color images into light and obtaining relatively high-quality color hard copies using photographic materials.
For example, instant photography using the color diffusion transfer method, in which images on a CRT are directly photographed through blue, green, and red filters, and 16-color images using three-color (blue, green, and red) gas lasers,
A method of recording on mm film is known (Television Society Journal, Vol. 36 (1), 50-50 (1982)).

However, instant photography using the color diffusion transfer method has problems with image quality, and gas lasers require a modulator to adjust the amount of light when irradiating photographic light-sensitive materials, and are relatively expensive and large. It has certain drawbacks.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an improved method of converting electrical signals into light and recording a color image on a photographic material, and a photographic material.

Another object of the present invention is to provide a method and a photographic material that can easily obtain images of relatively excellent quality in the above method.

Another object of the present invention is to provide a method and a photographic material in the above-mentioned method, in which a device (hereinafter referred to as an optical printer) for imparting image exposure to a photographic material can be made relatively compact.

Yet another object of the present invention is to provide, in the above system,
It is an object of the present invention to provide a method of making an optical printer at low cost and a photographic material.

Other objects of the invention will become apparent from the description.

The object of the present invention is to provide an organic silver salt oxidizing agent and an image dye containing spectrally sensitized photosensitive silver halide on a support, thereby imparting photosensitization and having different maximum spectral sensitization wavelengths. It has at least two types of heat-developable photosensitive layers containing donor compounds, and at least one of the photosensitive layers has maximum spectral increase in the infrared region of 700 nm or more and at least one has maximum spectral increase in the visible light region of 500 nm or more and less than 700 nm. A heat-developable color photographic light-sensitive material characterized by having a sensitive wavelength, and an image obtained by exposing the photographic light-sensitive material to light with a light-emitting diode or semiconductor laser having an emission wavelength within the spectral sensitization wavelength range of each of the above-mentioned light-sensitive layers and developing the image thermally. This is achieved by a forming method. In addition, the above infrared region is on the shortwave side.
up to 700 nm, preferably in the range of 700 to 1000 nm.

The above-mentioned image dye-providing compound is a compound that forms a dye upon exposure and thermal development depending on the amount of exposure, a dye that also discolors, a dye whose diffusivity or sublimation property changes, or such a dye. Compounds that can imagewise provide a dye upon imagewise exposure and thermal development.

In a preferred embodiment of the present invention, a heat-developable infrared-sensitive layer having a maximum spectral sensitization wavelength in the infrared region of 700 nm or more is provided on a support, in order from the side closest to the support, directly or intermediately on the layer. A heat-developable red photosensitive layer having a maximum spectral sensitization wavelength of 600 nm or more and less than 700 nm through a non-photosensitive layer such as a layer, and a heat-developable red photosensitive layer having a maximum spectral sensitization wavelength of 600 nm or more and less than 700 nm, and a heat-developable red photosensitive layer that has a maximum spectral sensitization wavelength of 500 nm or more directly or through a non-photosensitive layer such as an intermediate layer.
It has a heat-developable green photosensitive layer having a maximum spectral wavelength below 600 nm, and each photosensitive layer contains one of yellow, magenta and cyan dye-forming couplers different from those contained in the other photosensitive layers. Signals for blue, green, and red are written using a light-emitting diode (hereinafter referred to as an LED) or a semiconductor laser having an emission spectrum in each spectral sensitization wavelength range of the photographic light-sensitive material and each light-sensitive layer of the photographic light-sensitive material, and the blue, green, and red signals are written. A color image can be formed by using a yellow dye for green, a magenta dye for green, and a cyan dye for red by thermal development in proportion to or inverse proportion to the electric signal.

Another preferred embodiment of the present invention is a photographic light-sensitive material in which yellow, magenta and cyan dyes or compounds capable of releasing each of these dyes are separately contained in each light-sensitive layer similar to the above embodiment. A dye whose color fades in proportion to or inverse proportion to exposure, a dye whose diffusivity or sublimation changes in proportion to or inverse proportion to exposure, or a dye whose diffusivity or sublimation varies in proportion to or inverse proportion to exposure. Examples include a photographic light-sensitive material containing a compound capable of releasing , and a method of forming a color image using the photographic light-sensitive material in the same manner as in the above embodiment.

In addition, below, the region of 400 nm or more and less than 500 nm is the blue region, and the region of 500 nm or more and less than 600 nm is the green region.
The region of 600 nm or more and less than 700 nm is called the red region.

In the present invention, the silver halide of the spectrally sensitized photosensitive silver halide may be made from silver halide forming components known in the field of heat-developable light-sensitive materials, and the The dye-providing compound can be appropriately selected depending on the dye image forming method. Further, it is preferable that the heat-developable photosensitive layer contains a reducing agent according to a known technique.
The reducing agent may not be contained in the photosensitive layer in advance, but may be supplied from the outside before thermal development.

According to one embodiment of the present invention, for example, U.S. Pat.
Research Disclosure
Disclosure (hereinafter referred to as RD) 12146, 15108,
15127, JP-A No. 56-27132, etc., in which the color development method is applied, that is, reduction in which a dye is produced by reacting with a dye-forming coupler (hereinafter referred to as coupler) in an oxidized form. A reducing agent (such as a p-phenylenediamine or aminophenol developing agent) is contained in the heat-developable photosensitive layer, or such a reducing agent is present in the photosensitive layer during heat development, and is used as a dye image-providing compound. Embodiments using couplers are provided.

According to another embodiment of the present invention, an embodiment in which a method using a leuco dye described in, for example, U.S. Pat. No. 3,985,565, U.S. Pat.
That is, an embodiment is provided in which a colorless leuco dye is used as the dye image-providing compound and, if necessary, a cross-oxidizing developing agent is contained in the heat-developable photosensitive layer.

According to yet another embodiment of the present invention, a method using the silver salt dye bleaching method described in, for example, Japanese Patent Application Laid-open Nos. 52-105821 and 52-105822, etc. is applied, that is, thermal development. Embodiments are provided in which the photosensitive layer contains a reducing agent and a bleachable dye or dye precursor.

In addition to these embodiments of the present invention,
As described in RD15676, the dye is bleached by a reducing agent in the unexposed area; RD15126, 17706, etc., which are themselves reducing agents and are bleached in the exposed area; RD16966, 16967 It is also possible to apply an embodiment in which the organic silver salt is a silver salt of a dye and releases a diffusible dye upon development, and the technical configuration can be selected according to each method and technology. can.

The present invention is effective when using any of these methods, and in this case, for example, yellow dye,
The photosensitivity of the three types of heat-developable photosensitive layers that can control magenta and cyan dyes respectively are green sensitivity, red sensitivity, and infrared sensitivity (the combination of dye color and color sensitivity is arbitrary). good), each photosensitive layer green (500~600nm), red (600~700nm)
and infrared (700 to 1000 nm), respectively, using LEDs or semiconductor lasers with emission wavelengths.

Therefore, any component layer that contains a color component and records color development may be controlled by an LED having an emission wavelength in any spectral region, provided that the yellow component layer is emitted by an electric signal that controls blue.
The emission spectrum of the LED must match the spectral sensitivity, and the magenta component layer must have the same spectral sensitivity as the emission spectrum of the LED emitted by the electric signal that controls green. In addition, the cyan component layer must have a spectral sensitivity that matches the emission spectrum of an LED emitted by an electric signal that controls red. Therefore
As long as the three emission spectra of the LED do not overlap, for example, the yellow component layer is an infrared sensitive layer, the magenta component layer is a red sensitive layer, and the cyan component layer is a green sensitive layer. Write with LED, each LED
It is also conceivable to control it with blue, green, and red electrical signals, and other combinations are also conceivable.

However, JP-A-52-10582, JP-A No. 52-105822,
If the yellow component layer forming a yellow pigment, the magenta component layer forming a magenta pigment, and the cyan component layer forming a cyan pigment contain pigments having respective tones, as in RD16966 and RD16967, the pigments It is preferable to use a combination in which a layer having photosensitivity in the absorption wavelength range of is not located below the layer.
For example, if the magenta component layer is magenta in color, it is preferable not to be coated on the green photosensitive layer, and if the cyan component layer is also cyan in color, it is preferable not to be coated on the red photosensitive layer.

Furthermore, the photosensitivity of the yellow, magenta, and cyan component layers is not necessarily green (500~
600nm), red (600~700nm), infrared (700~
It is not necessary to set it to one of 1000nm; red (600~
700nm), Infrared-I (700-800nm), Infrared-
Combinations of photosensitivity (800 to 1000nm) are also possible, and in short, it is possible to have photosensitivity in each of the three non-overlapping regions from the visible region to the infrared region of 500nm or more, and then use the corresponding LED or semiconductor laser. All you have to do is write in combination.

Accordingly, in a preferred embodiment of the present invention, a heat-developable red colorant containing an organic silver salt, an infrared-sensitive silver halide emulsion, a cyan coupler, and a color developing agent is provided, for example, directly or via a subbing layer on a film support. An outer photosensitive layer, further directly or via an intermediate layer, a heat-developable red photosensitive layer containing an organic silver salt, a red-sensitive silver halide emulsion, a magenta coupler and a color developing agent, and further directly or via an intermediate layer an organic silver salt, a green-sensitive layer A heat-developable green photosensitive layer containing a silver halide emulsion, a yellow coupler and a color developing agent is sequentially coated. These heat-developable photosensitive layers convert red signals into infrared signals, green signals into red signals, and blue signals into green signals, respectively.
After writing by scanning exposure with LED, color development is performed by heat treatment. The color-developed sample is separated from the silver as a color image by commonly used bleach-fixing methods, diffusion transfer methods, etc., and a color hard copy can be obtained. U.S. Patent No.
Specifications of No. 3531286, No. 3761270, and No. 3764328,
Also RD12146, 15108, 15127, JP-A-1983-
Although an example has been shown of a typical configuration using a color heat development method using color development as described in Publication No. 27132, the present invention is not limited to this, and can be applied to various other heat development methods. Color schemes can also be used advantageously.

Examples of the photosensitive silver halide used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. The photosensitive silver halide can be prepared by any method known in the photographic field, such as a single-jet method or a double-jet method, but in particular, in the present invention, a silver halide gelatin emulsion is prepared. Light-sensitive silver halide emulsions prepared according to techniques including the following give favorable results.

The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include gold sensitization, ion sensitization, gold-
Various methods such as sulfur sensitization and reduction sensitization can be used.

The silver halide in the above photosensitive emulsion may have coarse or fine grains, but the preferred grain size is about 0.001 micron to 1.5 micron, more preferably about 0.01 micron to 0.5 micron.
It is micron.

The photosensitive silver halide emulsion prepared as described above can most preferably be applied to the heat-developable photosensitive layer which is a constituent layer of the photosensitive material of the present invention.

Furthermore, as another method for preparing photosensitive silver halide,
It is also possible to cause a photosensitive silver salt-forming component to coexist with an organic silver salt to form a photosensitive silver halide in a portion of the organic silver salt. The photosensitive silver salt-forming component used in this preparation method includes inorganic halides, such as
Halides represented by MX _o (where M represents an H atom, NH ₄ group or a metal atom, and X represents
Cl, Br or I, n indicates 1 when M is an H atom or an NH ₄ group, and indicates the valence when M is a metal atom. Metal atoms include lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, and lead. , antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium, osmium, iridium,
Examples include platinum and cerium. ), halogen-containing metal complexes (e.g. K ₂ PtCl ₆ , K ₂ PtBr ₆ , HAuCl ₄ ,
(NH ₄ ) ₂ IrCl ₆ , (NH ₄ ) ₃ IrCl ₆ , (NH ₄ ) ₂ RuCl ₆ ,
(NH ₄ ) ₃ RuCl ₆ , (NH ₄ ) ₃ RhCl ₆ , (NH ₄ ) ₃ RhBr ₆
), onium halides (e.g., quaternary ammonium halides such as tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide, tetraethylphosphonium bromide) Like 4
halogenated hydrocarbons (e.g. iodoform, bromoform carbon tetrabromide, 2-bromo-2-methylpropane) etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromphthalimide, N-bromoacetamide,
N-iodosuccinimide, N-bromphthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo- 4,4-dimethylhydantoin, etc.), and other halogen-containing compounds (for example, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.).

These photosensitive silver halides and photosensitive silver salt forming components can be used in combination in various methods, and the amount used is 0.001 mol to 1.0 mol, preferably 0.01 mol to 0.3 mol, per 1 mol of organic silver salt. It is.

Further, green-sensitive silver halide emulsions and red-sensitive silver halide emulsions used in each layer of the heat-developable color photographic light-sensitive material of the present invention, that is, the heat-developable green light-sensitive layer, the heat-developable red light-sensitive layer, and the heat-developable infrared light-sensitive layer, respectively. Silver emulsions and infrared-sensitive silver halide emulsions can be obtained by adding various spectral sensitizing dyes to the silver halide emulsions.

Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like. Among the cyanine dyes, those having a basic nucleus such as thiazoline, oxazoline, pyrroline, pyridineoxazole, thiazole, selenazole, and imidazole are more preferred. Such nuclei include alkyl groups, alkylene groups, hydroxyalkyl groups, sulfoalkyl groups,
It may contain carboxyalkyl groups, aminoalkyl groups or enamine groups capable of forming fused carbocyclic or heterocyclic rings. Moreover, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, phenyl group, enamine group, or heterocyclic substituent.

In addition to the above basic nucleus, merocyanine dyes have acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolidinedione nucleus, barbituric acid nucleus, thiazolinthione nucleus, malononitrile nucleus, and pyrazolone nucleus. Good too. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group, or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivatives, azaindene cadmium salts,
Organic sulfonic acids, etc., such as U.S. Pat. No. 2,933,390;
A supersensitizing additive that does not absorb visible light as described in the specification of No. 2937089 can be used in combination.

Particularly effective sensitizing dyes for the heat-developable photographic material of the present invention include JP-A Nos. 49-84637 and 49-84637;
No. 96717, No. 49-102328, No. 49-105524, No. 49-105524, No.
No. 50-2924, No. 50-29029, No. 50-104637,
No. 50-105127, No. 51-27924, No. 52-80829, British Patent No. 1467638, US Patent No.
4173478 can be effectively used, but among them, merocyanine dyes having a rhodanine nucleus, thiohydantoin or 2-thio-2,4-oxazolidinedione nucleus, such as 3-carboxymethyl-5-[ (3-Methyl-2-thiazolinylidene)-1-methylethylidene]rhodanine, 3-p-carboxy-phenyl-5-[β-
Ethyl-2-(3-benzoxazolylidene)ethylidene rhodanine, 5-](3-β-carboxyethyl-2-(3-thiazolinylidene)ethylidene)-3-ethylrhodanine, 1-carboxymethyl-5-[ (3-ethyl-2-(3H)-benzoxazolylidene)ethylidene]-3-phenyl-2-thiohydantoin, 3-ethyl-5[(3
-ethyl-2-benzothiazolinylidene)-1-
methylethylidene)-2-thio-2,4-oxazolidinedione, 3-alkyl-5-[3-ethyl-(2-naphthoxazolilidene)ethylidene-1-phenyl-2-thiohydantoin, 5-
(1-allyl-4(1H)-pyridylidene-3-carboxy-methylrhodanine, 5-(1-allyl-
4(1H)-pyridylidene)-3-carboxymethyl-2-thio-2,4-oxazolidinedione, 3
-carboxymethyl-5-[1,4-diethyl-
2-tetrazolin-5-ylidene)-ethylidene]
Rhodanine, 1,3-diethyl-5-[(3-ethyl-2-thiazolidinylidene)-1-(2-carboxyphenyl)-ethylidene]-2-thiohydantoin are effective; Compounds with tool acid nuclei, such as 1,3-diethyl-5
-[(3-ethyl-2-benzoxazolinylidene)ethylidene]-2-thiobarbituric acid, 1,
3-diethyl-5-[(1-ethyl-naphtho 1,
2,d thiazolin-2-ylidene)ethylidene]-2-thiobarbituric acid, and also merocyanine dyes with long chain alkyl substituents, such as 1,
3-diheptyl-[(3-ethyl-2-benzthiazolinylidene)ethylidene]-2-thio-barbituric acid and the like are effective. Furthermore, polynuclear merocyanine dyes such as those described in Japanese Patent Publication No. 49-18808 and US Pat. No. 3,877,943 are effective as sensitizing dyes in the red region, such as 3-ethyl-5-
[(1-Ethyl-1,2-di-hydroquinolinylidene)-2-ethylidene]-1-(3-carboxymethyl-4-oxo-2-thio-2-thiazolidinylidene)-4-thiazolidone , 3-n-heptyl-5-[(3-ethyl-2-benzothiazolinylidene)ethylidene]-2-(3-carboxymethyl-
4-oxo-2-thio-5-thiazolidinylidene)-4-thiazolidone, also 3-ethyl-5-
[(3-ethyl-4-methyl-4-thiazoline-2
-ylidene)ethylidene]-2-[(3-ethyl-
Examples include dyes such as 4,5-diphenyl-4-thiazolin-2-ylidene)methyl]-4-oxo-2-thiazolinium iodide. or
Infrared sensitizing dyes such as those described in RD15248 are effective in the present invention, such as 3,3'-diethyl-5,5'-diphenyl-thiatricarbocyanine ethyl sulfate, 1,1'- Diethyl
2,2'-dicarbocyanine-p-toluenesulfonate, 3,3'-diethylthiatricarbocyanine bromide, 3,3'-diethylselenatricarbocyanine bromide, 5-[4-(3-ethyl-
2-benzthiazolinylidene)-2-butenylidene]-3-heptyl-1-phenyl-2-thiohydantoin, 2,2'-diethyl-5-[1,3-
Bis{(1,3,3-trimethyl-2-idrinylidene)ethylidene}-2-cyclopentylidene}
-1,3-dioxane-4,6-dione and the like. Also, other polynuclear dyes, such as 3,6-
(3-Ethylbenzthiazolinylidenebutadienelidene)hexane-1,2,4,5-tetraone, etc. are also effective, as well as 4,4'-dicarbocyanines, 2,2'-tricarbocyanines, Also useful are thiatricarbocyanins, selenatricarbocyanins, and the like.

The amount of these dyes added is from 10 ^-4 mol to 1 mol per mol of silver halide or silver halide forming component. More preferably, it is 10 ⁻⁴ mol to 10 ⁻¹ mol.

Examples of organic silver salts used in the heat-developable color photographic material of the present invention include Japanese Patent Publication Nos. 43-4924 and 44
-26582, 45-18416, 45-12700, 45-18416, 45-12700,
No. 45-22185 and JP-A-49-52626, JP-A No. 52-
No. 31728, No. 52-13731, No. 52-141222, No. 53
-36224, 53-37610, U.S. Patent No.
Silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, etc., described in specifications such as No. 3330633 and No. 4168980, etc. Aromatic silver carboxylates such as silver benzoate, silver phthalate, etc., silver salts having an imino group such as silver benztriazole, silver saccharin, silver phthalazinone, silver phthalimide, etc., silver salts of compounds having a mercapto group or a thione group, etc. 2-mercaptobenz-oxazole silver, mercaptooxadiazole silver,
Silver mercaptobenzithiazole, silver 2-mercaptobenzimidazole, silver 3-mercapto-phenyl-1,2,4-triazole, and also 4-hydroxy-6-methyl-1,3,3a,
Examples include silver 7-tetrazaindene and silver 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene. Further, silver compounds such as those described in RD16966, RD16907, British Patent No. 1590956, and British Patent No. 1590957 can also be used. Among these, silver salts having an imino group, such as silver benztriazole, are preferred. Examples of silver salts of benztriazole include alkyl-substituted silver benztriazole, such as silver methylbenztriazole, silver bromo-benztriazole, and silver chlorobenztriazole. Halogen-substituted benztriazole silver such as triazole silver, amide-substituted benztriazole silver such as 5-acetamidobenztriazole silver, and compounds described in British Patent Nos. 1590956 and 1590957, such as N-[6 -chloro-4-N(3,5-dichloro-4-hydroxyphenyl)imino-1-oxo-5-methyl-2,
5-Cyclohexadien-2-yl]-5-carbamoylbenztriazole silver salt, 2-benztriazol-5-ylazo-4-methoxy-1-
Naphthol silver salt, 1-benztriazole-5-
Examples include ylazo-2-naphthol silver salt, N-benztriazol-5-yl-4-(4-dimethylaminophenylazo)benzamide silver salt, and the like.

Further, nitrobenztriazoles represented by the following general formula (I) and benztriazoles represented by the following general formula () can be advantageously used.

In the formula, R ¹ represents a nitro group, and R ² and R ³ may be the same or different and each represents a halogen atom (e.g., chlorine, bromine, iodine), a hydroxy group, a sulfo group, or a salt thereof (e.g., sodium salt, potassium salt, ammonium salt), carboxy group or its salt (e.g., sodium salt, potassium salt, ammonium salt), nitro group, cyano group, or carbamoyl group, sulfamoyl group, alkyl group, each of which may have a substituent. represents a group (e.g. methyl group, ethyl group, propyl group), an alkoxy group (e.g. methoxy group, ethoxy group), an aryl group (e.g. phenyl group) or an amino group;
m represents an integer from 0 to 2, and n represents an integer from 0 to 1. Examples of substituents for the carbamoyl group include a methyl group, ethyl group, and acetyl group. Examples of substituents for the sulfamoyl group include a methyl group, ethyl group, and acetyl group. Examples of substituents include a carboxyl group and an ethoxycarbonyl group, examples of substituents for an aryl group include a sulfo group and a nitro group, and examples of substituents for an alkoxy group include a carboxy group, an ethoxycarbonyl group, and an amino group. Examples of the substituent include an acetyl group, a methanesulfonyl group, and a hydroxy group.

The compound represented by the general formula (I) is a silver salt of a benzotriazole derivative having at least one nitro group, and specific examples thereof include the following compounds.

For example, 4-nitrobenzotriazole silver, 5
-Nitrobenzotriazole silver, 5-nitro-6
-chlorobenzotriazole silver, 5-nitro-6
-Methylbenzotriazole silver, 5-nitro-6
-methoxybenzotriazole silver, 5-nitro-
7-phenylbenzotriazole silver, 4-hydroxy-5-nitrobenzotriazole silver, 4-hydroxy-7-nitrobenzotriazole silver, 4
-Hydroxy-5,7-dinitrobenzotriazole silver, 4-hydroxy-5-nitro-6-chlorobenzotriazole silver, 4-hydroxy-5-
Nitro-6-methylbenzotriazole silver, 4-
Sulfo-6-nitrobenzotriazole silver, 4-
carboxy-6-nitrobenzotriazole silver,
5-Carboxy-6-nitrobenzotriazole silver, 4-carbamoyl-6-nitrobenzotriazole silver, 4-sulfamoyl-6-nitrobenzotriazole silver, 5-carboxymethyl-6-
Silver nitrobenzotriazole, Silver 5-hydroxycarbonylmethoxy-6-nitrobenzotriazole, Silver 5-nitro-7-cyanobenzotriazole, Silver 5-amino-6-nitrobenzotriazole, Silver 5-nitro-7-(p-nitrophenyl) )
Benzotriazole silver, 5,7-dinitro-6-
Examples include silver methylbenzotriazole, silver 5,7-dinitro-6-chlorobenzotriazole, and silver 5,7-dinitro-6-methoxybenzotriazole.

In the formula, R ⁴ has a hydroxy group, a sulfo group or a salt thereof (e.g., sodium salt, potassium salt, ammonium salt), a carboxy group or a salt thereof (e.g., sodium salt, potassium salt, ammonium salt), or a substituent. ^R5 represents a halogen atom (e.g. chlorine, bromine,
iodine), hydroxyl group, sulfo group or its salt (e.g. sodium salt, potassium salt, ammonium salt), carboxy group or its salt (e.g.
sodium salt, potassium salt, ammonium salt),
A nitro group, a cyano group, or an alkyl group (e.g., methyl group, ethyl group, propyl group), each of which may have a substituent, an aryl group (e.g., phenyl group), an alkoxy group (e.g., methoxy group,
ethoxy group) or amino group, p is 1
Alternatively, 2 and q represent an integer from 0 to 2.

Further, examples of substituents for the carbamoyl group in R ⁴ include a methyl group, ethyl group, and acetyl group, and examples of substituents for the sulfamoyl group include a methyl group, ethyl group, and acetyl group. can. Furthermore, examples of the substituent for the alkyl group in R include a carboxy group, ethoxycarbonyl group, etc., and examples of the substituent for the aryl group include a sulfo group, a nitro group, etc.
Examples of substituents for an alkoxy group include a carboxyl group and an ethoxycarbonyl group, and examples of substituents for an amino group include an acetyl group, a methanesulfonyl group, and a hydroxy group.

Specific examples of the organic silver salt represented by the general formula () include the following compounds.

For example, 4-hydroxybenzotriazole silver, 5-hydroxybenzotriazole silver, 4-hydroxybenzotriazole silver,
Silver sulfobenzotriazole, silver 5-sulfobenzotriazole, silver benzotriazole-4-sodium sulfonate, silver benzotriazole-5
- Sodium sulfonate, silver benzotriazole-4-potassium sulfonate, silver benzotriazole-5-potassium sulfonate, silver benzotriazole-4-ammonium sulfonate, silver benzotriazole-5-ammonium sulfonate, 4-
Silver carboxybenzotriazole, silver 5-carboxybenzotriazole, sodium benzotriazole-4-carboxylate, silver sodium benzotriazole-5-carboxylate, potassium silver benzotriazole-4-carboxylate, silver benzotriazole-5-carboxylic acid Potassium, silver benzotriazole-4-carboxylic acid ammonium, benzotriazole silver-5-carboxylic acid ammonium, 5-carbamoylbenzotriazole silver, 4
- Sulfamoylbenzotriazole silver, 5-carboxy-6-hydroxybenzotriazole silver, 5-carboxy-7-sulfobenzotriazole silver, 4-hydroxy-5-sulfobenzotriazole silver, 4-hydroxy-7-sulfobenzotriazole Silver, 5,6-dicarboxybenzotriazole silver, 4,6-dihydroxybenzotriazole silver, 4-hydroxy-5-chlorobenzotriazole silver, 4-hydroxy-5-methylbenzotriazole silver, 4-hydroxy-5-methoxy Benzotriazole silver, 4-hydroxy-5
-Silver nitrobenzotriazole, silver 4-hydroxy-5-cyanobenzotriazole, silver 4-hydroxy-5-aminobenzotriazole, silver 4-hydroxy-5-acetamidobenzotriazole, silver 4-hydroxy-5-benzenesulfonamide benzotriazole silver, 4-hydroxy-5-
Hydroxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-ethoxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-carboxymethylbenzotriazole silver,
4-Hydroxy-5-ethoxycarbonylmethylbenzotriazole silver, 4-hydroxy-5-phenylbenzotriazole silver, 4-hydroxy-
5-(p-nitrophenyl)benzotriazole silver, 4-hydroxy-5-(p-sulfophenyl)
Benzotriazole silver, 4-sulfo-5-chlorobenzotriazole silver, 4-sulfo-5-methylbenzotriazole silver, 4-sulfo-5-methoxybenzotriazole silver, 4-sulfo-5-cyanobenzotriazole silver, 4- Sulfo-5-aminobenzotriazole silver, 4-sulfo-5-acetamidobenzotriazole silver, 4-sulfo-5
-benzenesulfonamidobenzotriazole silver, 4-sulfo-5-hydroxycarbonylmethoxybenzotriazole silver, 4-sulfo-5-ethoxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-carboxybenzotriazole silver, 4-sulfo-5 -Carboxymethylbenzotriazole silver, 4-sulfo-5-ethoxycarbonylmethylbenzotriazole silver, 4-
Sulfo-5-phenylbenzotriazole silver, 4
-sulfo-5-(p-nitrophenyl)benzotriazole silver, 4-sulfo-5-(p-sulfophenyl)benzotriazole silver, 4-sulfo-5
-methoxy-6-chlorobenzotriazole silver,
4-Sulfo-5-chloro-6-carboxybenzotriazole silver, 4-carboxy-5-chlorobenzotriazole silver, 4-carboxy-5-methylbenzotriazole silver, 4-carboxy-5-
Nitrobenzotriazole silver, 4-carboxy-
5-aminobenzotriazole silver, 4-carboxy-5-methoxybenzotriazole silver, 4-carboxy-5-acetamidobenzotriazole silver, 4-carboxy-5-ethoxycarbonylmethoxybenzotriazole silver, 4-carboxy-
5-Carboxymethylbenzotriazole silver, 4
-Carboxy-5-phenylbenzotriazole silver, 4-carboxy-5-(p-nitrophenyl)
Examples include silver benzotriazole and silver 4-carboxy-5-methyl-7-sulfobenzotriazole. These compounds may be used alone or in combination of two or more.

The method for preparing the organic silver salt of the present invention will be described later, but the organic silver salt of the present invention may be isolated and used by dispersing it in a binder by an appropriate means, or it may be used by dispersing it in a binder using a suitable binder. A silver salt may be prepared therein and used as is without isolation.

The amount of the organic silver salt used is 0.05g to 1m of support.
10.0g, preferably 0.2g to 2.0g.

Further, examples of the reducing agent used in the heat-developable color photographic material of the present invention include US Pat. No. 3,531,286.
No. 3761270, No. 3764328, or
RD12146, RD15108, RD15127 and JP-A-56-
p-phenylenediamine type and p-aminophenol type developing agents, phosfluoramide phenol type and sulfonamide phenol type developing agents, and hydrazone type color developing agents described in Japanese Patent No. 27132 and the like can be advantageously used. In this case, a coloring dye is formed by oxidative coupling of the reducing agent with a coupler (coloring agent), a cyan dye is formed by coupling with a phenolic or naphthol compound, and a pyrazolone compound, a cyanoacetyl compound, or a pyrazolotriazole compound. Magenta dyes can be produced by coupling with active methylene-containing compounds such as intazole compounds and pyrazolobenzimidazole compounds, and magenta dyes can be produced by coupling with acetoacetanilide compounds, benzoylacetanilide, and pivaloylacetanilide compounds. A yellow pigment is formed.

Further, in the case of heat-developable color component layers of the type using leuco dyes described in U.S. Pat. No. 3,985,565, U.S. Pat. Alternatively, an acin-based reducing agent is used as the reducing agent, but these and the reducing agents described below can also be used in combination.

Other color methods include those using the SDB method and those in which the dye is bleached with a reducing agent in the unexposed (unconsumed) area, such as JP-A No. 52-10582,
There are systems such as JP 52-105822, US Pat. No. 4,235,957, RD18137, US Pat. No. 15126, US Pat. No. 15227, and US Pat. No. 15676, and the following reducing agents can be used.

That is, phenols (e.g., p-phenylphenol, p-methoxyphenol, 2,6-di-
tert-butyl-p-cresol, N-methyl-p
-aminophenol, etc.), sulfonamidophenols (e.g. 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dibromo-4-(p-
toluenesulfonamide) phenol, etc.), or polyhydroxybenzenes (e.g., hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone,
carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g.
α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.), hydroxybinaphthyls and methylene bisnaphthols (e.g. 1,1′-dihydroxy-2,2′-binaphthyl, 6,6′- dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6'-dinitro-
2,2'-dihydroxy-1,1'-binaphthyl,
4,4'-dimethoxy-1,1'-dihydroxy-
2,2'-binaphthyl, bis(2-hydroxy-1
-naphthyl)methane, etc.), methylenebisphenols (e.g., 1,1-bis(2-hydroxy-
3,5-dimethylphenyl)-3,5,5-trimethylhexane, 1,1-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy- 3,5-di-tert-butylphenyl)methane, 2,6-methylenebis(2-hydroxy-3-tert-butyl-
5-methylphenyl)-1-methylphenol,
α-phenyl-α,α-bis(2-hydroxy-
3,5-di-tert-butylphenyl)methane, α
-phenyl-α,α-bis(2-hydroxy-3
-tert-butyl-5-methylphenyl)methane 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-2-methylpropane, 1,1,5,
5-tetrakis(2-hydroxy-3,5-dimethylphenyl)-2,4-ethylpentane, 2,
2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-methyl-5-tert-butylphenyl)propane, 2,2-bis(4-hydroxy- 3,5
-di-tert-butylphenyl)propane, etc.), ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines.

Further, the reducing dye compound itself can be used as a reducing agent, and for example, dye developers such as those disclosed in processes such as RD15126 and RD17706 can also be used.

These reducing agents can be used alone or in combination of two or more. The amount of reducing agent used depends on the type of organic acid silver salt, photosensitive silver salt, and other additives used, but is usually 0.05 mol to 1 mol of organic acid silver salt. The amount ranges from 10 mol, preferably from 0.1 mol to 3 mol.

In addition to the above-mentioned components, various additives may be added to the heat-developable photographic material of the present invention, if necessary. For example, as a development accelerator, US Pat.
Alkali release agents described in the specifications of No. 3220846, No. 3531285, No. 4012260, No. 4060420, No. 4088496, No. 4207392, or RD15733, No. 15734, No. 15776, etc.; Organic acids described in -12700, non-aqueous polar solvent compounds having -CO-, -SO ₂ -, and -SO- groups described in U.S. Pat. No. 3,667,959, and melt foams as described in U.S. Pat. Examples include polyalkylene glycols described in U.S. Pat. In addition, as a color toning agent, for example, JP-A No. 46-4928, JP-A No. 46-6077,
No. 49-5019, No. 49-5020, No. 49-91215,
No. 49-107727, No. 50-2524, No. 50-67132,
No. 50-67641, No. 50-114217, No. 52-33722
No. 52-99813, No. 53-1020, No. 53-55115
No. 53-76020, No. 53-125014, No. 54-
No. 156523, No. 54-156524, No. 54-156525, No.
No. 54-156526, No. 55-4060, No. 55-4061, No.
Publications such as No. 55-32015 and West German Patent No. 2140406
No. 2147063, No. 2220618, U.S. Patent No.
Phthalazinone, phthalide, pyrazolone, quinazolinone, N- Hydroxynaphthalimide, benzoxazine, naphthoxazinedione, 2,3-dihydro-phthalazinedione, 2,3-dihydro-
1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline,
Aminoquinoline, isocarbostyryl, sulfonamide, 2H-1,3-benzothiazine-2,4
- (3H) dione, benzotriazine, mercaptotriazole, dimercaptotetrazapentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., mixtures of one or more of these with imidazole compounds, and phthalic acid, naphthalic acid Examples include a mixture of at least one acid or acid anhydride such as an acid and a phthalazine compound, and combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like. Also, 3-amino-5-mercapto-1,2,4 described in Japanese Patent Application No. 57-73215 and No. 57-76838
-triazoles and 3-acylamino-5-mercapto-1,2,4-triazoles are also effective.

In addition, as antifoggants, for example, Japanese Patent Publication No. 11113/1982, Japanese Patent Publication No. 90118/1973, Japanese Patent Publication No. 49-90118,
No. 10724, No. 49-97613, No. 50-101019, No. 49
-130720, 50-123331, 51-47419,
No. 51-57435, No. 51-78227, No. 51-104338
No. 53-19825, No. 53-20923, No. 51-
No. 50725, No. 51-3223, No. 51-42529, No. 51-
Publications such as No. 81124, No. 54-51821, and No. 55-93149, as well as British Patent No. 1455271 and US Patent No.
3885968, 3700457, 4137079, 4138265, and West German Patent No. 2617907, or oxidizing agents (for example, N-halogen Acetamide, N-
halogenosuccinimides, perchloric acid and its salts, inorganic peroxides, persulfates, etc.), or acids and their salts (such as sulfinic acid, lithium laurate, rosin, diterbenic acid, thiosulfonic acid, etc.),
Or sulfur-containing compounds (for example, mercapto compound-releasing compounds, thiouracil, disulfide, simple sulfur, mercapto-1,2,4-triazole, thiazolinthion, polysulfide compounds, etc.), others, oxazoline, 1,2,4-triazole, Examples include compounds such as phthalimide.

In addition, as a stabilizer, a printout preventive agent may be used at the same time, especially after processing.
No. 45228, No. 50-119624, No. 50-120328, No. 45228, No. 50-119624, No. 50-120328, No.
Halogenated hydrocarbons described in Publication No. 53-46020, specifically tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, 2-tribromo Methylsulfonylbenzothiazole, 2,4-bis(tribromomethyl)-
Examples include 6-methyltriazine.

Also, JP-A-46-5393, JP-A-50-54329,
Post-treatment may be performed using a sulfur-containing compound as described in each publication of No. 50-77034.

Furthermore, U.S. Patent No. 3301678, U.S. Patent No. 3506444
The isothiuronium-based stabilizer precursor described in the specifications of U.S. Pat. No. 3,824,103 and U.S. Pat. No. 3,844,788;
It may also contain activator stabilizer precursors and the like as described in No. 4,060,420 and the like.

In addition to the above-mentioned components, the heat-developable photosensitive material of the present invention further includes a binder, a spectral sensitizer, an antihalation dye, a fluorescent brightener, a hardener, an antistatic agent, a plasticizer, and a spreading agent. , etc., various additives, coating aids, etc. are added.

Various binders can be used in the heat-developable color photographic material of the present invention, and suitable binders include hydrophilic or hydrophobic binders depending on the purpose. For example, proteins such as gelatin and gelatin derivatives, cellulose derivatives, polysaccharites such as dextran, natural substances such as gum arabic, and latex-like vinyl compounds that increase the dimensional stability of photographic materials and synthetic polymers such as: include. As a suitable synthetic polymer, US special
Examples include those described in the specifications of No. 3142586, No. 3193386, No. 3062674, No. 3220844, No. 3287289, and No. 3411911. Useful polymers include alkyl acrylates,
Examples include water-insoluble polymers made of methacrylate, acrylic acid, sulboalkyl acrylate, or methacrylate. Suitable polymeric substances include polyvinyl butyral, polyacrylamide cellulose acetate butyrate, cellulose acetate propionate, polymethyl methacrylate, polyvinyl pyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride,
Chlorinated rubber polyisobutylene, butadiene styrene copolymer, vinyl chloride-vinyl acetate copolymer vinyl acetate-vinyl chloride-maleic acid copolymer, polyvinyl alcohol, polyvinyl acetate, benzyl cellulose, cellulose acetate, cellulose fropionate, cellulose acetate phthalate Can be mentioned. Among these polymers, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, and cellulose acetate butyrate are particularly preferred. If necessary, two or more types may be used in combination. The amount of the binder is 1/10 to 10 parts by weight, preferably 1/4 to 4 parts per part of organic silver salt for each photosensitive layer.

The layers containing the above components and other layers according to the present invention can be coated on a wide variety of supports. Supports used in the present invention include cellulose nitrate film, cellulose ester film,
Polyvinyl acetal film, polyethylene film, polyethylene terephthalate film,
Examples include plastic films such as polycarbonate films, glass, paper, and metals such as aluminum. Baryta paper and resin-coated water-resistant paper can also be used.

In addition to the photosensitive layer, the heat-developable photographic material used in the present invention may be provided with various layers such as an overcoat polymer layer, an undercoat layer, a backing layer, an intermediate layer, or a filter layer depending on the purpose.

The heat-developable photographic material produced in this manner is, for example, cut into a size suitable for use, and then imagewise exposed. Preheating (60 to 100°C) may be applied before exposure. The heat-developable color photographic material of the present invention is scanned and exposed using three color LED light sources as described above. The image-exposed photosensitive material is developed simply by heating (the development temperature is approximately 80-200°C, preferably 100-180°C). The heating time is arbitrarily adjusted, such as from 1 second to 60 seconds.

The heat-developable color photographic material can form a dye image by imagewise exposure and heat treatment, but these dye images can be bleach-fixed in a normal BF bath, washed with water, or as described in US Pat. No. 4,124,398 and the same. No.
It is possible to take out a dye image by thermally bleaching silver using the bleaching agent described in No. 4123273, and it is also possible to take out a dye image by thermally bleaching silver using a bleaching agent such as that described in the specification of No. 4123273. It can be thermally transferred using a hot solvent such as methyl anisate. It is also possible to use a thermal transfer method as described in British Patent No. 1590957.

In the heat-developable photographic material of the present invention, various mordants for dye images can be used as the image-receiving layer.
The image-receiving layer may also be a separate image-receiving element comprising the image-receiving layer on a suitable support, or the image-receiving layer may be a single layer that is part of the above-mentioned heat-developable photographic material element. good. If desired, an opacifying layer can be included in the photosensitive material element, such layer reflecting the desired degree of radiation, such as visible light, that can be used to observe the dye image in the image-receiving layer. is used for. The opacifying layer can contain various reagents to provide the necessary reflection, such as titanium dioxide.

A specific example of a semiconductor laser advantageously used in the heat-developable color photographic material of the present invention is Ga _1-x Al _x As/G _a As as a luminescent material/substrate combination.
(700~900nm), In1 _-x GaxAs1−yPy/InP (900~
1700 nm), In _1-x GaxAs ₁ −ySby/GaSb (1700~
Semiconductor lasers using materials such as 4000nm) can be mentioned. Semiconductor lasers that can be used as light sources for exposing the photosensitive material of the present invention include
It is a semiconductor laser with an oscillation wavelength of 1000 nm, and semiconductor lasers that are currently commercialized are semiconductor lasers with an oscillation wavelength of 700 to 1000 nm. Also, other than these specific examples,
Any semiconductor laser having an oscillation wavelength of 500 to 1000 nm can be advantageously used in the photosensitive material of the present invention.

The LED that can be advantageously used in the heat-developable color photographic material of the present invention is preferably an LED that emits light of 500 nm or more, and particularly preferred is an LED that emits light in the range of 500 to 1000 nm.

Specific examples of these LEDs include green-emitting LEDs.
GaP: N, YF ₃ : Yb, Er, yellow-emitting GaP:
NNGaAs _1-x Px: N, orange-emitting GaAs _1-x Px:
N, red-emitting Ga _1-x Al _x As, GaP:Zn, O,
Examples include LEDs using materials such as GaAs _1-x Px, infrared-emitting GaAs, and Ga _1-x Al _x As. In addition to these, the color photographic light-sensitive material of the present invention exhibits sufficient light emission in the 500 to 1000 nm region.
It goes without saying that LEDs can be advantageously used in the photosensitive material of the present invention.

Furthermore, when exposing the photosensitive material of the present invention using these LEDs or semiconductor lasers, it is necessary to expose the photosensitive material to an appropriate amount of light to obtain the desired image density after thermal development. One way to provide this appropriate amount of exposure is to electrically control the light emission of an LED or semiconductor laser. Various techniques are known in the art as methods for controlling the light emission of this LED or semiconductor laser, and these known techniques can be advantageously used to control the exposure of the photosensitive material of the present invention. Specific examples of these include methods of controlling the emission intensity by changing the current injected into the LED or semiconductor laser, or methods of controlling the total amount of light emission by controlling the number of emission pulses. Alternatively, there are various methods of combining the two, and these methods can be advantageously used in the photosensitive material of the present invention. Moreover, although only a very general example of controlling the light emission of an LED or a semiconductor laser is shown here, it goes without saying that other possible methods known in the art can be used. On the other hand, as another method for controlling the amount of light exposure to a photosensitive material without controlling the amount of light emitted by the LED or semiconductor laser, the light emission intensity of the LED or semiconductor laser remains constant and there is a A method of controlling the exposure amount by inserting a neutral density filter and changing the density of this filter, or by changing the scanning speed when scanning the light emitted from these light emitting elements onto the photosensitive material. , a method of controlling the amount of exposure to a photosensitive material, etc. In addition to these methods, the amount of exposure to the photosensitive material can be changed by various known methods.

Furthermore, when writing an image on the photosensitive material of the present invention with light using a light emitting element such as an LED or a semiconductor laser, it is necessary to apply an appropriate amount of exposure to obtain the desired image density at a predetermined position on the photosensitive material. There is. Obtaining this image-like image is achieved by scanning the light emitted from the light emitting element with respect to the photosensitive material and applying a predetermined amount of exposure to a desired position on the photosensitive material. This method of scanning can be accomplished by various techniques known in the art. Specific examples of these known methods include moving the photosensitive material in one direction with a roller or the like, passing the light emitted from the light emitting element through a lens and optical system in the direction of movement, and then using a rotating mirror or the like. A method in which the photosensitive material is exposed while being scanned, or a method in which the photosensitive material is wrapped around a rotating drum and exposed while being rotated while the light emitting element is scanned in the axial direction, or a method in which the photosensitive material is moved in one direction with a roller etc. A method in which light-emitting elements are exposed while reciprocating in a direction perpendicular to the direction, or a plurality of light-emitting elements are arranged in a linear array, and the photosensitive material is exposed while being moved in one direction with a roller or the like in a direction perpendicular to the straight line. method, or a combination of these methods. In addition to these methods, any scanning method known in the art can be advantageously used in the light-sensitive material of the present invention.

In addition, lenses, optical fiber concave mirrors, and the like can be advantageously used as a method for condensing light from a light emitting element in order to apply a predetermined amount of exposure to a predetermined position on the photosensitive material. Furthermore, in the case of using optical fibers, it is of course possible to simultaneously expose a plurality of locations by arranging a plurality of optical fibers in a straight line and combining them with a plurality of light emitting element arrays arranged in a straight line. As a means for exposing these photosensitive materials to light using a light emitting element, techniques known in the art regarding light amount adjustment, spatial scanning, etc. can be advantageously used.

Furthermore, the photosensitive material of the present invention is exposed to light of three different wavelengths, and these three types of exposure can be performed simultaneously or separately, depending on the light emitting element used. Determined by nature.

The present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Benztriazole silver 22.7g and alcohol 400%
ml, and 500 ml of 8% polyvinyl butyral aqueous solution (Eslec W-201, manufactured by Sekisui Chemical Co., Ltd.) was added and dispersed in a ball mill for 24 hours to prepare a dispersion. Next, while stirring this dispersion, a silver iodobromide emulsion (silver iodide 5 mol%, 60 g of gelatin and silver in 1 kg of emulsion) was prepared.
28 ml of cubic emulsion grains of average size 0.06 microns containing 0.353 moles) were added. Furthermore, as a sensitizing dye, 3-(3-ethylbenzthiazolinylidenebutadienylidene)-6-(3-ethylbenzthiazolinylidenehexatrienylidene)-hexane-1,
Add 9.0 ml of 0.05% by weight methanol solution of 2,4,5-tetraone, and add 8.2 g of p-amino-N,N-diethyl-aniline and 7.2 g of α-naphthol to 100 ml.
3-amino-
2 of 4-allyl-5-mercapto-triazole
Add 9 ml of % methanol solution and stir well. Apply the coating solution thus prepared to baryta paper with a dry film thickness.
It was applied to a thickness of 10 μm. After drying, an 8% polyvinyl butyral aqueous solution was applied as an intermediate layer to a dry film thickness of 8 μm, and then the above-mentioned 3-(3-ethylbenzthiazolinylidenebutadienelidene)-6-(3-ethylbenzthiazolinylidene)-6-(3-ethylbenzthiazolinylidene) was applied as a sensitizing dye. Thiazolinylidene-hexatrienylidene)-hexane-
3-carboxymethyl-5-[(N-ethylthiazolidine-2
-ylidene) ethylidene] - instead of 0.5 ml of 0.05% by weight methanol solution of rhodanine, coupler α
The same formulation except that 8.7 g of 1-phenyl-3-methylpyrazolone was used instead of naphthol was coated onto this to give a dry film thickness of 10 μm. First, the light emitted from a GaP green LED (Oki Electric OLD312) was focused on this sample to a diameter of 500 μm using a pinhole and a lens, and this light focusing spot was spread over a 50 mm x 10 mm screen on the sample per line (50 mm). 20 lines (0.5 mm per line) were scanned over a width of 10 mm at a scanning speed of 40 seconds. The driving current for the light emission of the LED (OLD312 manufactured by Oki Electric) was changed continuously from 0 mA to 30 mA for each scan. This sample was then heated at 150°C for 16
Developed for seconds. A cloudy magenta image was observed. Separately, a piece of paper (No. 2 manufactured by Toyo Paper Co., Ltd.) was soaked in methanol, placed over the resulting sample, passed through a hot roller at 60°C for 16 seconds, and then peeled from the sample to obtain a clear magenta wedge image on the paper. Next, the same exposure was performed by replacing the LED with an infrared light emitting diode (CLD222 manufactured by Oki Electric). Furthermore, same as above
The paper was developed at 150°C for 16 seconds, and the paper was placed on top of the sample obtained by soaking it in methanol and heated at 60°C for 16 seconds. A cyan wedge image was transferred onto the paper.

Example 2 Silver benztriazole in Example 1 was replaced with 24.3 g of silver hydroxybenztriazole, and p-amino-N,N-diethylaniline was replaced with 15.6 g of p-benzenesulfonamide-N,N-diethylaniline. A similar sample was prepared except that the lower layer coupler was 10.8 g of 5-acetamidonaphthol and the upper layer coupler was 8.6 g of 2-anilino-4-phenylthiazole. Exposure and development were carried out in the same manner as in Example 1. However, development was performed at 170°C for 16 seconds.

For transfer, instead of paper, as an image-receiving layer, copoly [styrene-(N-vinylbenzyl-N,N-dimethyl)ammonium chloride] was dispersed in gelatin and coated on baryta paper, which was then soaked in methanol. A clear wedge image of magenta to purple was transferred onto the image receiving layer by the green light emitting diode, and a clear wedge image of cyan color was transferred by the infrared light emitting diode onto the image receiving layer.

Example 3 First, coupler dispersions A and B were prepared according to the following procedure.

(Coupler dispersion A) 1-(2,4,6-trichlorophenyl)-3-
[3-(2,4-di-t-amylphenoxyacetamide)-benzamide]-2-pyrazoline-5-
A 5% aqueous solution of surfactant (Alkanol
The resulting mixture was dispersed in a colloid mill.

(Coupler dispersion B) 2-[4-(2,4-di-t-amylphenoxy)butylcarbamoyl]-1-naphthol
23.8 g, 20 g of dibutyl phthalate dissolved in 40 ml of ethyl acetate and 4% containing 7.5 ml of a 5% aqueous solution of surfactant (Alkanol Xc, manufactured by DuPont, USA)
After mixing with 300 ml of gelatin aqueous solution, it was dispersed in a colloid mill.

A multilayer color photographic material was then prepared according to the following recipe.

100 ml of alcohol and 400 ml of a 2% deionized gelatin aqueous solution were added to 24.3 g of 4-hydroxybenztriazole silver and dispersed in a ball mill for 24 hours to prepare a dispersion. Next, the following components were sequentially added to this dispersion while stirring to prepare a coating liquid.

(1) 300 ml of 10% deionized gelatin aqueous solution, (2) Silver iodobromide emulsion (silver iodide content 5 mol%, emulsion 1)
28 ml of cubic emulsion grains with an average diameter of 0.06 microns containing 60 g of gelatin and 0.353 mol of silver in kg), (3) 3-(3-ethylbenzthiazolinylidene-butadienylidene)-6-(3) as a sensitizing dye. −
9 ml of a 0.05 wt% methanol solution of ethylbenzthiazolinylidenehexatrienylidene) hexane-1,2,4,5-tetraone, and 300 ml of a separately prepared coupler dispersion B (4) (5) N-ethyl-N -methanesulfonamidoethyl-4-amino-3-methylaniline 13.5g,
12 ml of a 2% methanol solution of 3-amino-4-allyl-5-mercaptotriazole and a solution of 50 g of acetamide dissolved in 50 ml of water were added, and the mixture was coated on baryta paper and dried. Dry film thickness is 11μm
It was hot. Next, a layer consisting of gelatin, a spreading agent, and a hardening agent was applied to a thickness of 3 μm.

Further, as an upper layer, the sensitizing dye in the above composition was changed to 9 ml of a 2% methanol solution of 5-chloro-3,3'-sulfopropyl-9-ethyl-thiacarbocyanine, and the coupler dispersion was designated as dispersion A. A second layer was applied using the same recipe except for that. The total dry film thickness was 24 μm.

One of the samples was then given the same exposure as in Example 1. Another sample was similarly scanned using an infrared LED (OLD222 manufactured by Oki Electric) instead of the red LED. Each was heat developed at 140°C for 16 seconds. Cloudy magenta and cyan wedges were obtained, respectively. This was treated in a constant bleaching bath containing the following ingredients for 5 minutes, then washed with water and dried.

Ethylenediaminetetraacetic acid iron sodium salt
56g Ammonium thiosulfate 100g Sodium bisulfite 10g Ethylenediaminetetraacetic acid 18g Add water to 1 and adjust the pH to 7.0 with aqueous ammonia.

Clear wedge images of magenta and cyan were obtained, respectively.

Claims (1)

[Scope of Claims] 1. A support comprising an organic silver salt, an image dye-providing substance, and a spectrally sensitized photosensitive silver halide, and is photosensitive by the spectrally sensitized photosensitive silver halide. The maximum spectral sensitization wavelengths given are not the same,
It has at least two heat-developable photosensitive layers, and at least one of the photosensitive layers is in the infrared region of 700 nm or more, and at least one layer is in the infrared region of 500 nm or more and 700 nm.
1. A heat-developable color photographic material, which has a maximum spectral sensitization wavelength in a visible light region of less than or equal to 500 nm, and forms a cyan dye image by exposure and heat development of the infrared-sensitive layer. 2 Containing an organic silver salt, an image dye-providing substance, and a spectrally sensitized photosensitive silver halide on a support, the maximum spectral spectrum being imparted with photosensitivity by the spectrally sensitized photosensitive silver halide. The sensitizing wavelengths are not the same,
It has at least two heat-developable photosensitive layers, and at least one of the photosensitive layers is in the infrared region of 700 nm or more, and at least one layer is in the infrared region of 500 nm or more and 700 nm.
A heat-developable color photographic material having a maximum spectral sensitization wavelength in the visible light region of less than An image forming method characterized by exposing the image to light using a light emitting diode or a semiconductor laser each having an emission wavelength, and thermally developing the image.