JPH0336413B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a positive image forming method, and in detail,
A positive image forming method for obtaining a positive dye image by heating a silver halide photosensitive material having a silver halide emulsion layer containing at least a dye-providing substance and an internal latent image type silver halide whose surface is not coupled in advance. Regarding. [Prior art] As a photographic material using silver halide,
For example, a method using a dye formed by an oxidized color developing agent and a coupler, a method to obtain an image by bleaching the dye with silver (silver dye bleaching method), or a method using an oxidized ring element used in so-called instant photography. A method is known in which the released dye is diffused and transferred using an alkaline processing liquid. All of these methods perform image formation using alkaline or acidic processing liquids. In recent years, simple and rapid methods have been developed for these image forming methods that involve dry processing, such as heating, in a substantially water-free state. A heat-developable photosensitive material in which an image is formed by heat treatment and a processing method thereof are disclosed in U.S. Pat. No. 3,152,904;
No. 3301678, No. 3392020, No. 3457075 and Research Disclosure
Disclosure) No. 17029, June 1978 issue, pages 9-15. Regarding a method of obtaining a color image by heat development, a method of forming a color image by coupling with an oxidized product such as a developing agent is disclosed in US Patent No.
It is described in No. 3531286, No. 3761270, No. 4021240, Belgian Patent No. 802519, etc. However, this method has the disadvantage that a silver image and a color image after heat development occur simultaneously, making it impossible to obtain a clear color image. In order to solve this problem, some methods further carry out bleach-fixing treatment or silver bleaching using an activator sheet, but these are not preferred. On the other hand, a method is known in which a dye is liberated by thermal development using a dye silver salt, but the separation between exposed and unexposed areas is poor and a clear image cannot be obtained. Further, regarding the method of forming color images using leuco dyes, for example, US Pat. No. 3,985,565,
Although it is described in No. 4022617, it is difficult to stably incorporate leuco dyes into photographic materials.
It had the disadvantage of gradually becoming colored. On the other hand, regarding the method of forming a positive dye image, see, for example, Research Disclosure No. 14433, April 1976 issue.
Pages 30-32, issue 15227, December 1976 issue 14-15
Page, US Pat. No. 4,235,957, etc., describe heat-sensitive silver dye bleaching methods. However, this method requires extra steps and materials, such as stacking and heating activator sheets to accelerate the bleaching of the dye, and the resulting dye image is free from free particles that coexist during long-term storage. It had the disadvantage of being gradually reductively bleached by silver or the like. [Object of the Invention] Accordingly, a first object of the present invention is to provide a new method for forming a positive dye image by heating in a substantially water-free state. A second object of the present invention is to provide a method for obtaining clear positive dye images by a simple method. [Structure of the Invention] The object of the present invention is to provide a silver halide emulsion layer having a silver halide emulsion layer on a support containing at least a dye image-providing substance and an internal latent image type silver halide whose surface is not coupled in advance. A step of heating a photosensitive material in a range where no substantial development occurs after image exposure, a step of exposing the entire surface to light after or during the heating step, a step of thermally developing the material after the entire surface exposure, and a step of thermally developing the material by the action of heating. This was achieved by a positive imaging process comprising the step of transferring dye imagewise produced or released in said silver halide emulsion layer to an image receiving element. [Specific Structure of the Invention] Regarding the internal latent image type silver halide whose surface is not coupled in advance to be used in the present invention, for example, U.S. Pat.
No. 3511662, No. 3447927, No. 3761266,
As described in No. 3703584 and No. 3736140, it is a silver halide grain in which the sensitivity inside the grain is higher than the sensitivity on the surface of the grain. The method for producing silver halide emulsions containing these internal latent image type silver halides is as described in the above patent, for example, by first preparing AgCl grains and then adding bromide or a small amount of iodide thereto. A method in which the center core of chemically sensitized silver halide is coated with non-chemically sensitized silver halide, or a method in which chemically sensitized coarse grain emulsion and chemically sensitized Many methods are known, such as a method in which a fine grain emulsion which has not been chemically sensitized is mixed and a fine grain emulsion is deposited on a coarse grain emulsion. Also, U.S. Patent No. 3271157, U.S. Patent No. 3447927
Silver halide emulsions having silver halide grains containing polyvalent metal ions as described in US Pat. No. 3,531,291, or US Pat.
A silver halide emulsion in which the grain surface of silver halide grains containing a dopant is weakly chemically sensitized as described in JP-A-50-8524, JP-A-50-8524;
Silver halide emulsions comprising grains having a layered structure as described in No. 38525 and No. 53-2408;
Other JP-A-52-156614 and JP-A-55-
These include silver halide emulsions described in No. 127549. The silver halide emulsion containing internal latent image type silver halide used in the present invention (hereinafter referred to as internal latent image type silver halide emulsion) has a maximum density that can be achieved when developed with an "internal type" developer. is “surface type”
It can be further defined by saying that it is greater than the maximum density achieved when developed with a developer. The internal latent image type emulsion suitable for the present invention is prepared by coating the silver halide emulsion on a transparent support, exposing it to light for a fixed time of 0.01 to 1 second, and using the following "internal type" developer A. , the maximum density measured by the usual photographic density measurement method when developed at 20°C for 3 minutes is the same as that for silver halide emulsions exposed in the same manner as above at 20°C in the following "surface type" developer B. It has a density that is at least 5 times greater than the maximum density obtained when developed for 4 minutes. [Developer A] Hydroquinone 15g Metol 15g Anhydrous sodium sulfite 50g Potassium bromide 10g Sodium hydroxide 25g Sodium thiosulfate 20g Add water 1 [Developer B] p-Hydroxyphenylglycine 10g Sodium carbonate 100g Add water 1 The amount of internal latent image type silver halide used in the present invention is 0.001 g/m ² to 100 g/m ² in terms of silver.
The range is preferably 0.05g/m 2 , more preferably 0.05g/m ²
~50g/ ^m2 . The internal latent image type silver halide used in the present invention includes any halogenated silver halide such as silver chloride, silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, and silver iodide. I can give you silver. The average grain size of the silver halide is preferably from 0.001 μm to 2 μm, more preferably from 0.01 μm to 1 μm. Two or more types of silver halides having different sizes and/or halogen compositions may be used in combination. In the present invention, the average grain size means the grain diameter for spherical or approximately spherical silver halide grains, the edge length for cubic grains, and the same area as the projected area for silver halide grains other than spherical or cubic grains. The diameter of a circle is expressed as an average based on the particle size and projected area, respectively. The heat-developable silver halide photosensitive material according to the present invention (hereinafter referred to as the "heat-developable material") includes at least the internal latent image type silver halide whose surface is not coupled in advance on a support, and has a silver halide emulsion layer containing a dye image-forming substance that is chemically involved in this reaction and forms or releases a dye along with a silver image in the unexposed areas when silver halide is reduced to silver; If the heat-developable material is heat-developed, the produced or released dye and the unreacted dye image-providing substance coexist, which is not preferable for obtaining a clear dye image. Therefore, in the present invention, it is preferable that the dye imagewise generated or released by heat development is a diffusible dye, and by moving this diffusible dye to the dye-receiving layer, a material with excellent photographic properties can be obtained. A clear dye image can be obtained. This step is the "transfer step" in the present invention. The present invention is characterized by the internal latent image type silver halide whose surface is not coupled in advance as described above, and when the silver halide is reduced to silver by heating, it is chemically involved in this reaction and is not exposed to light. After imagewise exposure to a heat developable material having a silver image and a silver halide emulsion layer containing a dye-providing substance that generates or releases a diffusible dye in a portion thereof, the entire surface is exposed under or after heating, and then the entire surface is exposed to light. The purpose is to carry out heat development to transfer the diffusible positive dye image generated or released in the unexposed area to the dye-receiving layer. The dye-donating substance used in the present invention is
When the internal latent image type silver halide and/or the optionally used organic silver salt are reduced to silver under heated conditions, non-diffusible or diffusible dyes are chemically involved in this reaction. It is a compound that produces or releases . This generation or release reaction of non-diffusible or diffusible dyes is caused by the formation of fog nuclei in the internal latent image type silver halide when the internal latent type direct positive emulsion is subjected to image exposure, under heating, or after heating and then to full-scale exposure. This internal latent image type silver halide undergoes an oxidation-reduction reaction with a reducing agent or a reducing dye-donating substance, and (1) the reducing agent is oxidized to become an oxidized product, and this oxidized product reacts with the dye-donating substance and diffuses. (2) Reactions in which a reducing dye-donating substance is oxidized and a diffusible dye is released, etc. In particular, reactions (1) and (2) If an image-receiving material comprising an image-receiving layer suitable for receiving the diffusible dye produced by this process is brought into close contact with and superimposed on the heat-developable color photosensitive material having the dye-providing substance under heating, the image-receiving material in the image-receiving layer A dye positive image is obtained. On the other hand, (3) the internal latent image type silver halide and the reducing agent undergo an oxidation-reduction reaction to form a silver image, and then the remaining reducing agent and the dye-donating substance, which is non-diffusible at high temperatures, undergo an oxidation-reduction reaction. For example, the dye-donating substance described in JP-A No. 59-154445, or the dye-donating substance that releases a diffusible dye at high temperature, is oxidized and becomes non-diffusible. It is also possible to use the dye-providing substances described in, for example, JP-A-59-152440. However, in that case a dye image is obtained which is in a negative relationship to the silver image. As the dye-donating substance shown in the above (1), for example, JP-A-57-186744, JP-A-58-79247, JP-A-58-
No. 123533, No. 58-149046, No. 58-149047, No.
No. 59-12431, No. 59-48765, No. 59-159159,
No. 59-124339, No. 59-181345, Patent Application No. 1983-
No. 109293, No. 59-181604, No. 59-182507, No.
Compounds described in No. 59-179657 and No. 59-182506 are used. This compound is represented by the general formula A-L-B, and A
represents a coupler core having a substrate such as active methylene, active methine, phenol residue, naphthol residue, etc., which is oxidized and coupled with the oxidized form of the reducing agent, and L represents the bond between the oxidized form of the reducing agent and A. Represents a linking group in which the bond between A and L is broken during the reaction. When the carrier core A having the above-mentioned substrate is a dye-donating substance that has the function of releasing a diffusible dye by reacting with an oxidized form of a reducing agent, B represents a dye for forming a dye image or a dye precursor; The carrier core preferably has the ballast group to prevent the dye-donating substance itself from diffusing into other layers. On the other hand, in dye-donor materials that react with the oxidized form of the reducing agent to form a diffusible dye, B is a polymer derived from a ballast group or vinyl monomer that is large enough to prevent coupler diffusion. It is preferred that the carrier core A does not have anything that would impede the diffusion of the formed dye. Examples of the dye-donating substance shown in (2) above include JP-A No. 57-179840, JP-A No. 59-48764, JP-A No. 59-59-
No. 60434, No. 59-65839, No. 59-71046, No. 59
Compounds described in No. -87450, No. 59-88730, and No. 59-165055 are used. This compound has the general formula R-SO ₂ -D. R represents a reducible substrate that can be oxidized by silver halide, and D represents a dye or dye precursor for forming a dye image. Preferred reducing substrates include, for example, JP-A-57-179840, JP-A-58-58543, and JP-A-59.
−48764, and others.
U.S. Patent No. 4055428, U.S. Patent No. 3928312, U.S. Patent No.
No. 4076529, No. 4135929, No. 4258120, No. 4198235, No. 4273855, No. 4149892,
JP-A-53-46730, JP-A No. 56-12642, JP-A No. 56-
No. 16130, No. 56-16131, No. 57-650, No. 57-
Reducing substrates disclosed in No. 4043 and No. 57-85055 are used. The amount of the dye-providing substance used in the present invention is not limited, and depends on the type of the dye-providing substance, whether it is used alone or in combination, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or The amount may be determined depending on whether there are two or more layers, but for example, the amount used is 0.005 g to 10 g, preferably 0.1 g, per 1 m ² of the support.
g to 5.0 g can be used. Among the above-described dye-donating substances used in the present invention, preferable ones include hydrophilic groups such as sulfo groups and carboxy groups, which are described in detail in JP-A-59-124339 and JP-A-59-181345. It is preferable to have a group that immobilizes the dye-providing substance in the heat-developable photosensitive layer, such as a group, a hydrophobic ballast group with a large molecular weight, or a hydrophobic polymer residue.
It is preferable that the dye formed or released by heat development is heat transferable. The dye-providing substance particularly advantageously used in the present invention is a dye-forming compound represented by the following general formula (1). General formula (1) X-Y where X is a hydrophobic coupler residue,
This group does not include groups such as sulfo groups, carboxyl groups, thiosulfo groups, etc. that immobilize these dye-providing substances in the heat-developable photosensitive layer. Y is a group that can be separated from the coupler by a coupling reaction,
Also large hydrophobic groups such as sulfo, carboxyl, thiosulfo groups (e.g. 8 carbon atoms)
It has a group that immobilizes the dye-providing substance in the heat-developable photosensitive layer, such as the above-mentioned alkyl group, an aryl group having an alkyl group having 4 or more carbon atoms), or a hydrophilic or hydrophobic polymer residue. These dye-providing substances produce hydrophobic heat-transferable dyes through a coupling reaction with an oxidized form of a reducing agent formed by heat development. For example, X is represented by the following general formula (2). Groups represented by -(6) are preferred. In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom, or an iodine atom), or an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms). , for example methyl,
ethyl, butyl, t-octyl, n-dodecyl,
Examples include groups such as n-pentadecyl and cyclohexyl, but examples of alkyl groups substituted with aryl groups, such as phenyl groups, may include benzyl groups and phenethyl groups. ), substituted or unsubstituted aryl groups (e.g. phenyl, naphthyl, tolyl, methyl), acyl groups (e.g. acetyl, tetradecanoyl, pivaloyl, substituted or unsubstituted benzoyl), alkyloxy carbonyl group (e.g. methoxycarbonyl group, benzyloxycarbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group, p-tolyloxycarbonyl group, α-naphthoxycarbonyl group), alkylsulfonyl group) (e.g. methyl sulfonyl group), arylsulfonyl group (e.g. phenylsulfonyl group),
Carbamoyl group (e.g. substituted or unsubstituted alkylcarbamoyl group, methylcarbamoyl group,
Butylcarbamoyl group, tetradecylcarbamoyl group, N-methyl-N-dodecylcarbamoyl group, optionally substituted phenoxyalkylcarbamoyl group, specifically 2,4-di-t-aminophenoxybutylcarbamoyl group , substituted or unsubstituted phenylcarbamoyl group, specifically 2-
dodecyloxyphenylcarbamoyl group, etc.), substituted or unsubstituted acylamino group (e.g. n-
Butyramide, laurylamide, optionally substituted β-phenoxyethylamide group, phenoxyacetamide group, substituted or unsubstituted benzamide group, methanesulfonamidoethylamide group, β
-methoxyethylamide group), alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, e.g. methoxy group, ethoxy group, octadecyloxy group), sulfamoyl group (e.g. methylsulfamoyl group, n-dodecylsulfamoyl group) group, substituted or unsubstituted phenylsulfamoyl group, specifically dodecyl phenylsulfamoyl group),
Represents a sulfonylamino group (eg, methylsulfonylamino group, tolylsulfonylamino group) or a hydroxyl group. Further, R ₁ and R ₂ may be combined with each other to form a saturated or unsaturated 5- to 6-membered ring. Furthermore, R ₅ , R ₆ and R ₇ are a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 22 carbon atoms, such as a methyl group or an ethyl group). , an alkoxy group (preferably an alkoxy group having 1 to 2 carbon atoms, such as a methoxy group or an ethoxy group), a substituted or unsubstituted alkylamide group (such as a laurylamide group),
It also represents a phenoxyalkylamide group that may be further substituted (for example, an alkyl-substituted phenoxyacetamide group), a substituted or unsubstituted arylamide group, and the like. Further, R ₈ is an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms, such as a methyl group, a butyl group, or a heptadecyl group), an alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, such as a methoxy group, ethoxy group, octadecyloxy group),
Arylamino groups (e.g. anilino groups, further substituted with substituents such as halogen atoms, alkyl groups, amido groups or imido groups), substituted or unsubstituted alkylamide groups (e.g. laurylamide groups further substituted) phenoxyacetamide group, phenoxybutanamide group),
It represents a substituted or unsubstituted arylamide group (for example, a benzamide group, and a benzamide group further substituted with a halogen atom, an alkyl group, an alkoxyamide group, etc.). Further, R ₉ represents an alkyl group (preferably an alkyl group having 1 to 18 carbon atoms) or a substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, methoxyphenyl group, etc.). Furthermore, R ₁₀ represents an arylamino group (for example, an anilino group, or an anilino group substituted with a halogen atom, an alkyl group, an alkoxy group, an alkylamido group, an arylamido group, an imido group, etc.). A coupler residue represented by X These substituents R ₁ to _{R 10} preferably have an aryl group having an alkyl group having 8 or more carbon atoms and/or an alkyl group having 4 or more carbon atoms so as not to impede the thermal transferability of the formed dye. In the general formula (1), Y is a hydrophilic group such as a sulfo group or a carboxy group, or a group represented by -JZ (where J is a divalent bonding group and Z is a substituted or unsubstituted group). represents an alkyl group or an aryl group.)
More specifically, the divalent bonding group represented by J is -O-, -S-,

【formula】

【formula】

[Formula] -N=N-, -NHSO-, -O-SO ₂ -, etc. can be mentioned,
The alkyl group or aryl group represented by Z is preferably an alkyl group or aryl group substituted with a hydrophilic group such as a sulfo group or a carboxyl group. Among them, an alkyl group substituted with an alkylcarbamoyl group or an arylcarbamoyl group that may be further substituted, an alkyl group substituted with a carbalkoxy group, a carboaryloxy group, an alkyl group substituted with a halogen atom,
Also, an aryl group substituted with an optionally substituted alkylamide group, alkylsulfonamide group, arylamide group, arylsulfonamide group, etc.
an optionally substituted alkylcarbamoyl group, an alkylsulfamoyl group, an arylcarbamoyl group, an arylsulfamoyl group, an aryl group substituted with a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms; an aryl group substituted with an alkyl group having 1 to 22 carbon atoms, an aryl group substituted with an alkylamino group having 1 to 22 carbon atoms, others, halogen atoms, hydroxyl groups, sulfo groups, carboxy groups, An aryl group substituted with a sulfamoyl group or the like is particularly preferred. The active point substituent as represented by Y described in detail above includes hydrophilic groups such as sulfo groups and carboxyl groups, and carbon atom groups in order to immobilize the entire coupler molecule against heat within the containing layer. It is preferable to have a group that immobilizes the dye-providing substance, such as an aryl group having an alkyl group of 8 or more or an alkyl group of 4 or more carbon atoms, and it is more preferable that these hydrophilic groups are It is more preferable to have both an alkyl group having 8 or more carbon atoms or an aryl group having an alkyl group having 4 or more carbon atoms. Among the above-mentioned hydrophilic groups, particularly preferred are sulfo group, sulfino group, sulfeno group,
Thiosulfo group, dithiosulfo group, hydroxysulfonyloxy group, hydroxysulfonylthio group,
These include a carboxyl group, a thiocarboxy group, etc., and are described in detail in the above-mentioned JP-A-59-181345. Also, Japanese Patent Application Publication No. 58-149047, Japanese Patent Application No. 1987-109293,
No. 59-179657, No. 59-181604, No. 59-182507
It is also preferable to use a coupler having a polymer chain as a ballast group as described in No. 59-182506. The dye-providing substance of the present invention can be introduced 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 esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate) , benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc. Solvents, or organic solvents with a boiling point of about 30°C to 160°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-
After dissolving in ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Further, dispersion methods using polymers described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be used. The amount of the high boiling point organic solvent used in the present invention is preferably 10 g or less, more preferably 5 g or less per 1 g of the dye-providing substance used. In the present invention, the optical fogging method that provides full-surface exposure used in the full-surface exposure step is based on the formation of fog nuclei by photodecomposition of silver halide, so the type of silver halide used,
It is preferable to change the appropriate exposure intensity or amount depending on the characteristics, the number of layers, the layer structure, etc. of the silver halide photosensitive material. For example, Tokuko Sho 45-12709
No. 1 discloses a method of uniformly exposing the entire surface of the heat-developable photosensitive material according to the present invention to low-intensity light during the heat development process. This results in a good direct positive image with high maximum density and low minimum density. However, after image exposure of a heat-developable multicolor light-sensitive material consisting of two or more uncoupled internal latent image type silver halide emulsion layers on a support, each of which is not sensitive to the same wavelength range, it is difficult to process the material during the heat development process. As described above, under the condition that the entire surface is uniformly exposed to light of low intensity, it is difficult to obtain satisfactory image characteristics in all of the formed images of the plurality of layers. When such an internal latent image type direct positive color heat-developable multicolor photosensitive material is developed using a photofogging method, in order to obtain a good positive color image, it must be exposed to relatively low intensity light in a limited range. It is necessary. That is, a heat-developable multicolor photosensitive material consisting of two or more uncoupled internal latent image type silver halide emulsion layers, each of which is not sensitive to the same wavelength region, on a support is used to directly obtain a positive image using a photofogging method. In this case, good positive color images are obtained by providing a total exposure in which the ratio of the photographic intensity of the total exposure to each of the silver halide emulsion layers is preferably not greater than 6. The term "photographic strength" used here refers to the strength that can exert a photographic effect on a silver halide emulsion layer that has been fully exposed, and is determined relative to each silver halide emulsion layer. can do. Photographic strength depends on the energy distribution of full-surface exposure and the spectral sensitivity distribution of each silver halide emulsion layer. The photographic intensity ratio is determined, for example, by the method described in JP-A-58-70223. The light source for full-surface exposure used in the present invention can be any one as long as it can be adjusted so that the relative photographic intensity ratios for each layer of the silver halide color light-sensitive material used are preferably not greater than 6. It can be used with anything. For example, tungsten lamps, fluorescent lamps, halogen lamps, xenon lamps, mercury lamps, sunlight, etc. can be used, or a combination of these can also be used. The ratio of the photographic intensities of the entire surface exposure can be changed in a commonly known manner so as to satisfy the above conditions. The energy distribution of the light source itself can be changed, and filters such as color correction filters and color density conversion filters can also be used. The entire surface exposure can also be performed using multiple light sources. In a preferred example, blue light, green light,
A separate light source for each red light can be used to provide a full exposure. When a plurality of light sources are used, the entire surface exposure time may be the same for the plurality of light sources, or may be exposed at different times. The entire surface exposure of the present invention can also be carried out by the method described in Japanese Patent Laid-Open No. 127587/1983, in which optical fog is eliminated while increasing the exposure illuminance. In the present invention, the entire surface exposure is performed after the image exposure of the photographic light-sensitive material;
It is carried out during or after heating a silver halide emulsion having latent image nuclei therein at a moderately elevated temperature, for example at about 80°C to about 200°C for about 0.5 seconds to about 300 seconds. . In the heat-developable material used in the present invention, development is caused by heating, and after the image exposure of the heat-developable material, the photosensitive layer is heated to a temperature within the above range to sensitize it. The entire surface is exposed immediately before or at the same time as the temperature in the material becomes constant and development begins. Alternatively, after heating the heat-developable material at a low temperature at which no development occurs, the temperature may be left as it is or after it has been lowered to room temperature, the entire surface may be exposed to light, and the temperature may be subsequently increased to a temperature at which development begins. In this case, the time until the entire surface is exposed can be arbitrarily selected as long as the heat-sensitive material undergoes a heating step. It is preferable to carry out the heating and full-surface exposure at the same time. In this case, the full-face exposure is performed when the heat-developable material is heated and the temperature within the photosensitive layer containing the internal latent image type silver halide emulsion reaches the heating temperature. From the viewpoint of photographic properties, it is preferable to carry out full-surface exposure when the photosensitive layer is in a dry state containing substantially no water.
It is preferable to carry out the process after a second or more has elapsed. As long as the temperature applied to the heat developable material is within the above range, either high or low temperatures can be used by increasing or shortening the heating time.
A temperature range of 110°C to about 160°C is useful. Heating means in the heating process include heating by passing between hot plates or contacting with hot plates, heating by rotating a hot roll or drum while heating, heating by passing through a heated cavity, and other heating methods such as rollers, belts, or Heating by placing the guide member along the heat source can be used. Furthermore, heating may be performed by high frequency heating or laser beam. Also, as described in Japanese Patent Application Laid-Open No. 59-77442,
The heat-transferable material may have a conductive heating layer made of a conductive material such as graphite, carbon black, or metal that heats the photosensitive layer by generating heat when electricity is applied from the electrodes; in that case, 1. After exposing the photosensitive material, electricity is applied to the conductive heating layer of the heat developable material to heat it and expose the entire surface to light to complete development and transfer. 2. After exposing the photosensitive layer of a heat-developable material having an internal latent image type direct positive silver halide emulsion and a conductive heat-generating layer, the conductive heat-generating layer is heated to an extent that development does not substantially proceed. At the same time,
Alternatively, after heating, the entire surface is exposed to light to release the diffusive dye from the unexposed area, and then the image-receiving material is superimposed and the generated dye is transferred onto the image-receiving material. 3. After exposure, the conductive heating layer of the heat developable material is overlaid with the image-receiving material and heated to such an extent that the dye is not substantially released, and then or simultaneously, the entire surface of the photosensitive layer is exposed to active light. After that, it is heated again to generate a diffusible dye in the unexposed area,
A method that can be used includes moving and transferring the diffusible dye generated in the unexposed area to the image-receiving material, and then peeling the image-receiving material from the sensitive material to obtain a color positive image. In the present invention, at least a dye-providing substance, a photosensitive layer having an internal latent image type silver halide emulsion whose surface is not coupled in advance, and a dye-receiving layer to which a generated or released dye is transferred are formed on the same support. Alternatively, they can be formed on separate supports. The dye-receiving layer and photosensitive layer can also be peeled off. For example, after image exposure, the entire surface is exposed while being heated, and further heating is continued or heat development is carried out at a high temperature, so that the dye generated or released along with the silver image in the unexposed area is diffused and transferred from the photosensitive layer to the dye image-receiving layer. , and then the dye-receiving layer or photosensitive layer can be peeled off. In addition, when a photosensitive material with a photosensitive layer coated on a support and an image receiving material with a dye-receiving layer coated on a support are formed separately, the photosensitive material is imagewise exposed and heated uniformly, and then the entire surface is coated. Exposure to light, then heat development to produce or release a diffusive dye from the dye-providing substance along with a silver image in unexposed areas by the action of heating, and then an image-receiving material is superimposed to produce or release a photosensitive layer. The dye thus obtained can be transferred to a receiving layer. Alternatively, only the photosensitive material may be imagewise exposed and heated uniformly, and then the image-receiving material may be superimposed and the entire surface exposed to light for heat development. Furthermore, only the light-sensitive material may be imagewise exposed, then the image-receiving material is superimposed and uniformly heated, and then the entire surface is exposed and the dye is diffused and transferred to the dye-receiving layer by heat development. If the photosensitive material and image-receiving material are already integrated into a close-contact body, image exposure is performed through one of the supports of the two materials, and the subsequent steps are performed to obtain a positive dye image on the image-receiving material. You can also do it. Image exposure or full-surface exposure after heating is performed from the front surface (photosensitive layer side) or rear surface of the photosensitive material. When image exposure or whole surface exposure after heating is performed through one support of the adherent body, the support is preferably transparent, but is not necessarily limited to a transparent support as long as the exposure dose is increased. When the surface of the light-sensitive material and the dye-receiving surface of the dye-receiving material are brought into close contact with each other and heated after image exposure, or after heating at the same time as image exposure and full-surface exposure, the heating is applied only to the diffusion and movement of the dye. The heating temperature and heating time can be set independently of the heating for development. When this method is employed, it is preferable that the heating for development completes the reaction for development within a short period of time so as not to contribute to the diffusion and movement of the dye as much as possible. On the other hand, the heating to transfer the image-wise released dye to the dye-receiving layer should be kept as low as possible within a reasonable transfer time so as not to cause a thermal reaction in the unexposed areas. preferred for obtaining. In the positive image forming method of the present invention, the diffusion movement of the dye produced or released in the photosensitive layer may be started at the same time as the production or release of the dye, or after the production or release of the dye is completed. Therefore, the heating for the diffusion and movement of the dye may be performed after the heat development or at the same time as the heat development. Simultaneously with thermal development means that heating for development also acts as heating for diffusional movement of the dye produced or released at the same time. The optimum temperature for forming fog nuclei on the surface of internal latent image type silver halide during or after heating, the optimum temperature for development, and the optimum temperature for the diffusion and movement of dyes, and the requirements for each. Since the heating times may not always be the same, it is preferable to set the temperatures independently. In a preferred embodiment of the present invention, an organic silver salt coexists with internal latent image type silver halide that has not been fogged in advance.
It is a relatively light-stable, colorless, white, or light-colored silver salt that reacts with a reducing agent to form a silver image when heated to 80°C or higher, preferably 100°C or higher. Examples of organic silver salts that can be preferably used in the photosensitive material of the present invention include Japanese Patent Publication No. 43-4924, Japanese Patent Publication No. 44-26582,
No. 45-18416, No. 45-12700, No. 45-22185, and JP-A-49-52626, No. 52-31728, No. 52
−13731, No. 52-141222, No. 53-36224, No.
53-37610, U.S. Patent No. 3330633, U.S. Patent No. 3330633,
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. 4168980, and aromatic carboxylic acids silver, such as silver benzoate, silver phthalate, etc., silver salts having an imino group, such as silver benzotriazole, silver saccharin, silver phthalazinone, silver phthalimide, etc.; silver salts of compounds having a mercapto group or a thione group, such as 2- Silver mercaptobenzoxazole, silver mercaptooxadiazole, silver mercaptobenzothiazole, silver 2-mercaptobenzimidazole, 3-mercapto-phenyl-
1,2,4-triazole silver, and also 4-hydroxy-6-methyl-1,3,3a,7
-tetrazaindene silver, 5-methyl-7-hydroxy-1,2,3,4,6-bentazaindene silver, and the like. Also RD16966, RD16907, British Patent No. 1590956
It is also possible to use silver compounds such as those described in No. 1,590,957. Among these, silver salts having an imino group such as benzotriazole silver salts are preferred, and examples of benzotriazole silver salts include alkyl-substituted benzotriazole silvers such as methylbenzotriazole silver, e.g. bromo-benzotriazole silver, halogen substituted benzotriazole silver such as chlorbenzotriazole silver, amide substituted benzotriazole silver such as 5-acetamidobenzotriazole silver,
In addition, compounds described in British Patent No. 1590956 and British Patent No. 1590957, such as N-[6-chloro-4
-N(3,5-dichloro-4-hydroxyphenyl)imino-1-oxo-5-methyl-2,5-
cyclohexadien-2-yl]-5-carbamoylbenzotriazole silver salt, 2-benzotriazol-5-ylazo-4-methoxy-1-naphthol silver salt, 1-benzotriazol-5-ylazo-2-naphthol silver salt, Examples include N-benzotriazol-5-yl-4-(4-dimethylaminophenylazo)benzamide silver salt. Further, nitrobenzotriazoles represented by the following general formula (7) and benzotriazoles represented by the following general formula (8) can be advantageously used. General formula (7) In the formula, R ₁₁ represents a nitro group, R ₁₂ and R ₁₃
may be the same or different, and each represents a halogen atom (e.g. chlorine, bromine, iodine), a hydroxy 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), nitro group, cyano group, or carbamoyl group, sulfamoyl group, alkyl group (e.g. methyl group, ethyl group, propyl group), alkoxy group (e.g. methoxy group, ethoxy group), aryl group (e.g. phenyl group) or amino group;
m represents 0 to 2, and n represents 0 or 1. Further, examples of substituents for the carbamoyl group include methyl group, ethyl group, acetyl group, etc., and examples of substituents for sulfamoyl group include methyl group, ethyl group, acetyl group, etc. Examples of substituents for alkyl groups include carboxy groups and ethoxycarbonyl groups; examples of substituents for aryl groups include sulfo groups and nitro groups; examples of substituents for alkoxy groups include carboxy groups and ethoxycarbonyl groups. and as a substituent for the amino group, for example, an acetyl group,
Examples include a methanesulfonyl group and a hydroxy group. The compound represented by the general formula (7) 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-
Chlorbenzotriazole 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. General formula (8) In the formula, R ₁₄ 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. _R15 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 alkyl group which may have a substituent (e.g. methyl group, ethyl group, propyl group), aryl It represents a group (for example, phenyl group), an alkoxy group (for example, methoxy group, ethoxy group), or an amino group, p is 1 or 2, and q is an integer of 0 to 2. Further, examples of substituents for the carbamoyl group in R ₁₄ include methyl group, ethyl group, acetyl group, etc., and examples of substituents for sulfamoyl group include methyl group, ethyl group, acetyl group, etc. be able to. Furthermore, the R
Examples of substituents for alkyl groups include carboxy groups and ethoxycarbonyl groups; examples of substituents for aryl groups include sulfo groups and nitro groups; and examples of substituents for alkoxy groups include carboxy groups and ethoxycarbonyl groups. Examples of the groups and substituents of the 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 (8) include the following compounds. For example, 4-hydroxybenzotriazole silver,
5-Hydroxybenzotriazole silver, 4-sulfobenzotriazole silver, 5-sulfobenzotriazole silver, benzotriazole silver-4-sodium sulfonate, benzotriazole silver-5-sodium sulfonate, benzotriazole silver-4
-Potassium sulfonate, silver benzotriazole-
Potassium 5-sulfonate, silver benzotriazole-4-ammonium sulfonate, silver benzotriazole-5-ammonium sulfonate, silver 4-carboxybenzotriazole, silver 5-carboxybenzotriazole, silver benzotriazole-4
- Sodium carboxylate, silver benzotriazole-5-sodium carboxylate, silver benzotriazole-4-potassium carboxylate, silver benzotriazole-5-potassium carboxylate, silver benzotriazole-4-carboxylate ammonium, silver benzotriazole-5 - ammonium carboxylate,
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-methoxybenzotriazole silver, 4-hydroxy-5-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-
benzenesulfonamide benzotriazole 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-(4-nitrophenyl)benzotriazole silver, 4-carboxy-5-methyl-
Examples include silver 7-sulfobenzotriazole. Even when used alone, these compounds
Two or more types may be used in combination. The organic silver salt that can be preferably used in combination with the present invention can be prepared by a known method, and the organic silver salt can be isolated and used by dispersing it in a binder by an appropriate means, or A silver salt may be prepared and used as is without isolation. The amount of the organic silver salt used is preferably 0.01 mol to 500 mol, more preferably 0.1 mol to 100 mol, per 1 mol of silver halide. The average particle size of organic silver salts is about 10 μm to approx.
0.01 μm is preferred, more preferably about 5 μm to about
It is 0.1 μm. As a reducing agent that is oxidized by an internal latent image type silver halide and/or an organic silver salt used in combination as necessary, and has the ability to form or release a dye by reacting with a dye-donating substance, an oxidation coupling agent is used. Color developing agents that form dye images are useful. As such a reducing agent, for example, JP-A-56
-146133, 4-N,N-dialkyl phenyl sulfamic acids, N,N-diethyl-p-phenylenediamine, N-phenyl-N
So-called p-phenylenediamine color developing agents such as N,N-dialkyl-p-phenylenediamines such as -isopropyl-p-phenylenediamine and the like are used, as described in US Pat. No. 3,531,286. In addition, for example, 4-amino-2,6-dichlorophenol, 4-amino-2
-Methylphenol sulfate, 4-amino-
Aminophenols such as 2,6-dichlorophenol hydrochloride are also preferably used. Furthermore, phenolic reducing agents such as 2,6-dichloro-4-substituted sulfonamide phenol, 4-
Naphthol reducing agents such as amino-naphthol derivatives and 4-substituted sulfonamide naphthol derivatives, aminohydroxypyrazole derivatives described in U.S. Pat. No. 2,895,825, U.S. Pat. No. 2,892,714
Aminopyrazoline derivatives described in Research Disclosure No. 19412 and No.
19415 (June 1980 issue) are useful. These reducing agents may be used alone or in combination of two or more including the above-mentioned reducing agents. The reducing agent used in the present invention is used within a certain concentration range. The concentration range of the useful reducing agent is preferably 0.01 mol to 1500 mol, more preferably 0.1 mol to 200 mol per mol of internal latent image type silver halide. In addition to the above-mentioned reducing agents, the following reducing agents can also be used as auxiliary developers. Useful auxiliary developers include hydroquinone, t-
Alkyl-substituted hydroquinones such as butylhydroquinone and 2,5-dimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, alkoxy-substituted hydroquinones such as methoxyhydroquinone, polyhydroxy such as methylhydroxynaphthalene, etc. There are benzene derivatives. Furthermore, methyl gallate, ascorbic acid, ascorbic acid derivatives, N,N'-di-(2
Hydroxylamines such as -ethoxyethyl) hydroxylamine, 1-phenyl-3-pyrazolidone and 4-methyl-4-hydroxymethyl-1-
Pyrazolidones such as phenyl-3-pyrazolidone, reductones, and hydroxytetronic acids are useful. The auxiliary developer used in the present invention can be used within a certain concentration range. A useful concentration range is preferably from 0.01 mol to 1500 mol, more preferably from 0.1 mol to 200 mol, per mol of silver halide. Various binders can be used in the photosensitive 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, polysaccharides 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: contains. Suitable synthetic polymers include U.S. Pat. Nos. 3,142,586 and 3,193,386.
No. 3062674, No. 3220844, No. 3220844, No. 3062674, No. 3220844, No.
Examples include those described in the specifications of No. 3287289 and No. 3411911. Useful polymers include water-insoluble polymers based on alkyl acrylates, methacrylates, acrylic acid, sulboalkylacrylates or methacrylates. Suitable polymeric substances include polyvinyl butyral, polyacrylamide, cellulose acetate butyrate, cellulose acetate propionate, polymethyl methacrylate, polyvinylpyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride, chlorinated rubber, polyisobutylene, butadiene styrene copolymer, vinyl chloride-vinyl acetate copolymer,
Examples include vinyl acetate vinyl chloride-maleic acid copolymer, polyvinyl alcohol, polyvinyl acetate, benzylcellulose, cellulose acetate, cellulose propionate, and cellulose acetate phthalate. 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. In the present invention, the binder is preferably a hydrophilic binder. Here, "hydrophilic" means something that is soluble in water or a mixed solution of water and an organic solvent (a solvent that can be mixed with water). Examples of hydrophilic binders include gelatin, derivatives, cellulose derivatives, polysaccharides such as dextran, natural substances such as gum arabic, etc. and useful polymers such as polyvinyl acetal (preferably with a degree of acetalization below 20%,
Examples include polyvinyl butyral), polyacrylamide, polyvinylpyrrolidone, ethyl cellulose, and polyvinyl alcohol (preferably one with a saponification degree of 75% or more). These may be used in combination of two or more types, if necessary. The amount of the binder is preferably 0.01 to 100 times the internal latent image type silver halide in each photosensitive layer.
More preferably, it is 0.05 to 50 times, and support 1
A range of 0.2 to 50 g (total amount of binder of each layer added) per m ² is preferred. After the photothermographic material of the present invention is imagewise exposed,
An imagewise distribution of a thermally transferable dye is formed from the dye-providing material by thermal development, and at least a portion of the imagewise distribution is transferred to an image receiving member in a stacked relationship with the light-sensitive material to form a color image. to form. The dye can be transferred to the image receiving member by various methods, such as transfer using an organic solvent such as methanol, acetonitrile, dimethylformamide, etc., or water, thermal transfer using a hot solvent, or thermal transfer by sublimation of the dye itself. A transfer method can be used, but if the photosensitive material contains a thermal solvent, the dye can be transferred simply by bringing the photosensitive material into close contact with the image receiving member and heating it. The image-receiving member used in the present invention only needs to have the function of receiving the dye released or formed by thermal development, and can be used as a mordant used in dye diffusion transfer type light-sensitive materials or as described in JP-A No. 57-207250. It is preferable to use a heat-resistant organic polymer material having a glass transition temperature of 40° C. or higher and 250° C. or lower. Specific examples of the mordants include nitrogen-containing secondary and tertiary amines, nitrogen-containing heterocyclic compounds, quaternary cationic compounds thereof, US Pat. No. 2,548,564,
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in US Pat.
Polymers containing dialkylamino groups disclosed in US Pat. No. 2,882,156; Aminoguanidine derivatives disclosed in US Pat. No. 2,882,156;
covalently reactive polymers as described in No. 317333;
Mordants capable of crosslinking with gelatin, etc., disclosed in U.S. Patent Nos. 3625694 and 3859096, British Patent Nos. 1277453 and 2011012, and U.S. Patent No.
Aqueous sol type mordant disclosed in No. 3958995, No. 2721852, and No. 2798063, JP-A-1988-
61228, U.S. Pat. No. 3,788,855, West German Patent Application (OLS) No.
No. 2843320, Japanese Patent Publication No. 53-30328, No. 52-155528
No. 53-125, No. 53-1024, No. 54-74430
No. 54-124726, U.S. Patent No. 55-22766, U.S. Patent No. 3642482, U.S. Patent No. 3488706, U.S. Patent No. 3557066,
No. 3271147, No. 3271148, Special Publication No. 1971-
No. 29418, No. 56-36414, No. 57-12139,
Examples include various mordants disclosed in RD12045 (1974). Particularly useful mordants are polymers containing ammonium salts, such as those containing quaternary amino groups as described in US Pat. No. 3,709,690. For example, as a polymer containing an ammonium salt, polystyrene coated
In N,N,N-tri-n-hexyl-N-vinylbenzylammonium chloride, the ratio of styrene and vinylbenzylammonium chloride is:
Preferably 1:4 to 4:1, more preferably 1:
It is 1. A typical image-receiving layer for dye diffusion transfer is obtained by coating a polymer containing an ammonium salt mixed with gelatin on a support. Examples of the heat-resistant organic polymer substances include polystyrene with a molecular weight of 2,000 to 85,000, polystyrene derivatives having a substituent having 4 or less carbon atoms, polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, and polyvinyl. Alcohol, polyacetals such as polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polyoxyfluorinated ethylene, polyacrylonitrile, poly-N,N-dimethylallylamide, p-cyanophenyl group, pentachlorophenyl group, and Polyacrylate with 2,4-dichlorophenyl group, polyacryl chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, poly-tert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene Glycol dimethacrylate, poly-2-
Examples include polyesters such as cyano-ethyl methacrylate and polyethylene terephthalate, polycarbonates such as polysulfone, bisphenol A, and polycarbonate, polyanhydrides, polyamides, and cellulose acetates. Also, Polymer Handbook 2nd ed. (J.
Brandrup, EHImmergut (ed.) John Wiley &
Glass transition temperature listed in Sons Publishing, 40
Synthetic polymers at temperatures above 0.degree. C. are also useful. These polymeric substances may be used alone or in combination of two or more as a copolymer. Particularly useful polymers include cellulose acetate, such as triacetate and diacetate;
Terephthalic acid with heptamethylene diamine, adipic acid with fluorene dipropylamine, hexamethylene diamine diphenic acid, polyamide with combinations such as hexamethylene diamine and isophthalic acid, diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxib Examples include polyester made from a combination of tan and ethylene glycol, polyethylene terephthalate, polycarbonate, and vinyl chloride. These polymers may be modified. For example, cyclohexanedimethanol, isophthalic acid, methoxypolyethylene glycol, 1,
Polyethylene terephthalate using 2-dicarbomethoxy-4-benzenesulfonic acid or the like as a modifier is also effective. Among these, particularly preferred are the layer made of polyvinyl chloride described in Japanese Patent Application No. 58-97907, and the layer made of polycarbonate and a plasticizer described in Japanese Patent Application No. 58-128600. The above polymer is used by dissolving it in a suitable solvent and coating it on a support to form an image receiving layer, or by laminating a film-like image receiving layer made of the above polymer on a support, or by coating it on a support. It is also possible to constitute the image-receiving layer solely from a member (for example, a film) made of the above-mentioned polymer (combined image-receiving layer/support type). Further, the image-receiving layer may be constructed by providing an opaque layer (reflective layer) containing titanium dioxide or the like dispersed in gelatin on the image-receiving layer on a transparent support. This opaque layer provides a reflective color image when the transferred color image is viewed from the transparent support side of the image-receiving layer. The internal latent image type silver halide emulsion in the present invention is disclosed in, for example, US Pat. No. 1,623,499, US Pat.
For example, the use of chemical sensitizers such as sulfur, selenium, tellurium compounds, gold, platinum compounds, reducing agents such as tin halides, or a combination thereof, as described in the specifications of No. 3297447. Therefore, it may be chemically sensitized. Further, the internal latent image type silver halide emulsion in the present invention includes, for example, cyanine dyes, merocyanine dyes,
Optically sensitized using optical sensitizing dyes such as complex cyanine dyes, complex merocyanine dyes, holoporacyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc., either singly or in combination of two or more. Also good. Furthermore, ascorbic acid derivatives, azaindene, cadmium salts,
Additives such as organic onium salts and organic sulfonic acids, which do not absorb visible light and have a supersensitizing effect, such as those described in US Pat. No. 2,933,390 and US Pat. No. 2,937,089, can also be used. Regarding sensitizing dyes, see Research Disclosure No.
15162 (November 1976). Various methods can be used in combination to prevent thermal fog in the photothermographic material used in the practice of the present invention. One method is to use benzotriazole and its derivatives, thiouracils, mercapto compounds such as 1-phenyl-5-mercaptotetrazole, azole thioethers, or blocked azolethiones, and disulfides such as persulfates. , for example, N-halogenosuccinimide, N-halogenoacetamide, N-halogenoxazolinone, N-halogenobenzotriazole, N-halogenobenzimidazole, etc.
Halogen compounds can also be used. Other methods for preventing heat fog include, for example, higher fatty acids such as lauric acid, myristic acid, and behenic acid, tetrahalogenophthalic acid or its anhydride, arylsulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid, Aryl sulfinic acids such as p-toluenesulfinic acid, or salts thereof, lithium salts of higher fatty acids such as lithium laurate, lithium myristate, and lithium behenate can be used as stabilizers. In addition, salicylic acid, p-hydroxybenzoic acid,
Acid stabilizers such as substituted benzoic acids such as tetrachlorobenzoic acid and p-acetamidobenzoic acid, phthalic acid, isophthalic acid, trimetic acid, pyromethic acid, and 5,5'-methylenebissalicylic acid are also effective. Examples of color toning agents that can be used in the heat-developable material used in the present invention include JP-A-46-1928 and JP-A-46-1928;
No. 6077, No. 49-5019, No. 49-5020, No. 49-
No. 91215, No. 49-107727, No. 50-2524, No. 50
-67132, 50-67641, 50-114217, 50-67641, 50-114217,
No. 52-33722, No. 52-99813, No. 53-1020, No. 52-99813, No. 53-1020, No.
No. 53-55115, No. 53-76020, No. 53-125014,
No. 54-156523, No. 54-156524, No. 54-156525
No. 54-156526, No. 55-4060, No. 55-4061
No. 55-32015, as well as West German patent no.
2140406, 2147063, 2220618, U.S. Patent No. 3080254, 3847612, U.S. Pat.
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, which is a compound described in the specifications of No. 3782941, No. 3994732, No. 4123282, No. 4201582, etc. , 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., and a mixture of one or more of these with an imidazole compound, or an acid such as phthalic acid, naphthalic acid, or mixtures of at least one acid anhydride and a phthalazine compound, as well as phthalazine and maleic acid, itaconic acid, quinolinic acid,
Examples include combinations of gentisic acid and the like. Also, Japanese Patent Application Laid-open No. 58-189628 by the present applicant,
3-amino-5-mercapto-1,2,4-triazoles, 3-acylamino-5-mercapto-1,
2,4-triazoles are also effective. The internal latent image type photosensitive silver halide emulsion used in the present invention suppresses surface sensitivity as low as possible,
To provide lower minimum concentrations and more stable properties, e.g. thiazolium salts, azaindenes (typically 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1- It is preferable to add antifogging and stabilizing agents such as phenyl-5-mercaptotetrazole), urazole, sulfocatecol, oxime, nitrone, nitroindazole, and the like. Regarding these, for example, U.S. Patent No.
It is described in the specifications of No. 2728663, No. 2839405, No. 2566263, No. 2597915, and British Patent No. 623448. The internal latent image type silver halide emulsion used in the present invention includes, for example, wetting agents such as hydroxyalkanes, copolymers of alkyl acrylates or alkyl methacrylates with acrylic acid or methacrylic acid, and styrene-semi-alkyl maleic anhydride. Film property improvers such as water-dispersible particulate polymeric substances obtained by emulsion polymerization such as ester copolymers, coating aids such as saponin, polyethylene glycol lauryl ether, etc., thickeners, and antistatic agents. agents, gelatin plasticizers, surfactants, PH regulators, antioxidants, ultraviolet absorbers, dyes, brighteners, mordants, and, for example, starch,
The addition of various photographic additives such as matting agents such as titanium dioxide, zinc oxide, silica, alumina, kaolin, clay, polymer beads such as polymethyl methacrylate, etc. is optional. The photographic constituent layers of the heat-developable photosensitive material used in the practice of the present invention can be hardened with various organic or inorganic hardeners. Suitable hardeners include, for example, chromium salts, zirconium salts, aldehydes such as formaldehyde and mucohalogen acids, halotriazine hardeners, polyepoxy compounds, ethyleneimine hardeners, vinyl sulfone hardeners, isocyanate hardeners, carbodiimide hardeners, and acryloyl hardeners. Examples include film agents. The photographic constituent layer containing each component used in the heat-developable photosensitive material used in the present invention is coated on various supports selected from a wide variety of materials. Generally, this support may be of any shape, but it is preferable to use a support that is visible in handling as an information recording material, and therefore a film or sheet is usually used. Materials for the support include cellulose nitrate, cellulose ester (partially acetylated versions of these are also good), plastic films or sheets such as polyvinyl acetal, polyethylene, polyethylene terephthalate, polycarbonate, and polyimide, glass, paper, Examples include films and sheets made of metals such as aluminum. Furthermore, baryta paper, resin coated paper, and water-resistant paper can also be used. As the paper support, clay-treated paper such as art paper or coated paper is most suitable, and paper sized with polysaccharide or the like may also be used. In addition to coating these supports with the various layers described above, the supports themselves can also contain some of the components. Of course, when a component is mixed into a support such as plastic, glass, or metal, there are many difficulties in fully demonstrating its function, but for example, in the case of a paper-based support, Even if a certain component is mixed into the support (paper base material), it will exhibit the same effect as when it is present in a layer coated on the support. Whether the components are contained in the support or in the coated layer on the support can be easily implemented depending on various conditions such as the intention of the practitioner of the present invention and necessity and advantage in manufacturing. can do. The heat-developable photosensitive material used in the practice of the present invention is
Various additional additives may be used to enhance the resulting image density. For example, U.S. Pat.
-CO-, such as tetrahydrothiophene-1,1-dioxide, 4-hydroxybutanoic acid lactone, methylsulfinylmethane, sulfamide derivatives, as described in No. 3667959 and JP-A-59-84236; Compounds having groups such as -SO- or _-SO2- are effective. The above compounds can be used in a wide range of applications.
The useful range is preferably 20% or less of the dry coated film thickness of the photosensitive material, more preferably 0.1 to 15% by weight. Other useful salts include zinc, cadmium, and copper acetates, such as those described in US Pat. No. 3,708,304. In particular, base-releasing compounds that become alkaline when heated, such as acid salts of amines, metal oxides, or hydroxides, and base-releasing compounds that become alkaline when heated, such as NH ₄ Fe (SO ₄ ) ₂ 12H ₂ O, etc. Water-releasing compounds that release water are also useful as materials that promote development and dye-releasing reactions. These accelerators can be used in a wide range of ways. The useful range is preferably 50% by weight or less of the dry coated film thickness of the photosensitive material, more preferably,
It ranges from 0.01 weight percent to 40 weight percent. In addition, U.S. Patent No. 3347675, Japanese Patent Application Publication No. 59-57231
Polyglycols, ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, etc. described in No. 59-168439 are solid at room temperature, but the treatment used Preferably, non-hydrolyzable thermal solvents are used which exhibit a mixed melting point together with the other components at the temperature. The photographic constituent layers of the heat-developable photosensitive material used in the present invention are prepared by preparing respective coating solutions and sequentially coating them on a support by various coating methods such as dipping, air knife, curtain coating, or hopper coating. A photosensitive material can be created by drying. Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095. [Specific Effects of the Invention] As explained above, in the present invention, a silver halide photosensitive material having an emulsion layer containing at least a dye-providing substance and an internal latent image type silver halide on a support is prepared after image exposure. , a step of heating, a step of full exposure, a step of developing, and a step of transferring the dye imagewise formed or released in the emulsion layer by the action of heating to the image-receiving element, so that it is substantially free of water. We were able to provide a method for obtaining clear positive dye images using a simple method. [Specific Examples of the Invention] The present invention will be described below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 [Preparation of internal latent image type silver halide emulsion] An internal latent image type silver halide emulsion is prepared according to the method described in JP-A-55-127549. That is, potassium chloride containing 10g of gelatin.
To 220 ml of a 1.2 molar aqueous solution, 200 ml of a 1 molar aqueous solution of silver nitrate was quickly added at 40°C. After physical ripening for 10 minutes, 200 ml of a 1.2 molar aqueous solution of potassium bromide was added to obtain convergence type silver chlorobromide particles. The pH of the latent silver chlorobromide emulsion thus prepared was adjusted, and excess salt was removed by sedimentation and washing with water. Thereafter, the pH was adjusted to 6.0 to obtain a silver chlorobromide emulsion with a yield of 400 g. [Preparation of sulfobenzotriazole silver emulsion] Dissolve 40 g of poly(4-vinylpyrrolidone), 30 g of 4-sulfobenzotriazole, and 6 g of sodium hydroxide in a mixed solvent of 150 ml of water and 150 ml of ethanol, and add 5N to the mixture while stirring. Silver nitrate aqueous solution 30
ml, adjust the pH to 6-8, add water and adjust the total volume.
An organic silver salt dispersion liquid was obtained in a volume of 600 ml. [Preparation of gelatin dispersion of dye-providing substance] 30 g of the following dye-providing substance C-1 was dissolved in 26 g of dioctyl phthalate and 96 g of ethyl acetate, and a 1.7% aqueous gelatin solution containing 80 ml of a 5% aqueous solution of Alkanol XC (manufactured by DuPont) was prepared. 350 ml and dispersed with an ultrasonic homogenizer to prepare an oil-in-water dispersion of the dye-providing substance. [Preparation of heat-developable photosensitive material A-1] The following composition containing the internal latent image silver halide emulsion prepared above, sulfobenzotriazole silver as an organic silver salt, and a gelatin dispersion of a dye-providing substance was prepared as follows. did. [Photosensitive coating composition A-1] (a) Internal latent image type silver chlorobromide emulsion 50 g (b) Gelatin dispersion of dye-providing substance C-1 40 ml (c) 4-sulfobenzotriazole silver salt dispersion Liquid 40ml (d) Sodium 4-(diethylamino)-2-methylphenylsulfamate 0.5g (e) Gelatin 2g (f) 3-Methyl-1,3,5-pentanetriol
6 g (g) Development accelerator 3% aqueous solution 5ml (h) Surfactant 5% aqueous solution 2ml (i) Hardener 3% aqueous solution 5ml (j) Water 10ml or more (a) to (j) are mixed, Maintain at 35℃±1℃, PH
5.5, the amount of silver was deposited on a polyethylene terephthalate film with a 150μm thickness undercoating process.
It was applied at a concentration of 1.1 g/m ² . [Preparation of heat-developable color photosensitive material A-2] Instead of the dispersion of dye-providing substance C-1 used in the heat-developable photosensitive material A-1, 4 g of the dye-providing substance Y-1 below was mixed with ethyl acetate. Dissolve in 12ml,
This solution was mixed with 30 ml of a 2.5% aqueous gelatin solution containing a surfactant, water was added to make 60 ml, and the mixture was dispersed with an ultrasonic homogenizer to prepare the following composition containing a dispersion of a dye-donating polymer as follows. . [Photosensitive coating composition A-2] (a') Internal latent image type silver chlorobromide emulsion sample (same as A-1) 50 g (b') Gelatin dispersion of dye-providing substance Y-1
40ml (c') 4-Sulbenzotriazole silver salt dispersion
40ml (d') 4-(diethylamino)-2-methylphenylsulfamic acid sodium 0.5g (e') Gelatin 2g (f') Polyvinylpyrrolidone (average molecular weight 30,000)
3g (g') Polyethylene glycol (molecular weight) 3g (h') 3-methyl-1,3,5-pentanetriol 3g (i') Water Mix 10ml or more of (a') to (i') and prepare the sample. It was coated onto a 150 μm thick polyethylene terephthalate film in the same manner as A-1 so that the amount of silver was 0.95 g/m ² . Photothermographic materials A-1 and A obtained above
-2 was imagewise exposed to tungsten light through a sensitometry light wedge, then heated on a heat block heated to 150°C, and 10 seconds after the start of heating, the tungsten light was used as the light source and an exposure intensity of 100 lux was applied. After exposing the entire surface to light for a second, the temperature was returned to room temperature. Next, polyvinyl chloride-containing latex NIPOL G-576 (manufactured by Nippon Zeon Co., Ltd.) was coated on photographic baryta paper and passed through an atmosphere of 150°C to form a smooth film. The above fully exposed heat-developable photosensitive materials were stacked so that the film surfaces were in contact with each other, and heat development was performed at 150°C for 1 minute using a commercially available heat development device Copymate Model (manufactured by Graphics Products Inc.). After that, the image-receiving material was immediately peeled off, and a positive cyan transfer color image was obtained from the photothermographic material A-1, and a positive yellow transfer color image was obtained from the photothermographic material A-2. The reflection density of this positive image is measured using the densitometer, Sakura densitometer PDA-
Table 1 shows the results of measuring the maximum density (Dmax) and minimum density (Dmin) using 65 (manufactured by Konishiroku Photo Industry Co., Ltd.).

[Table] As is clear from the results in Table 1, it can be seen that good dye images can be obtained with the samples of the present invention. Example-2 In place of the dye-providing substance C-1 used in the heat-developable photosensitive material A-1 of Example-1, 30 g of the following reducing dye-providing substance M-1 was added to dioctyl phthalate 30
g and 90 ml of ethyl acetate, mixed with an aqueous gelatin solution containing a surfactant, and then dispersed with an ultrasonic homogenizer to prepare 500 ml of an oil-in-water dispersion of the dye-providing substance. The following composition containing this dispersion was prepared as follows. [Photosensitive coating composition A-3] (a″) Internal latent image type silver chlorobromide emulsion (same as sample A-1) 60 g (b″) Dispersion of dye-providing substance M-1 50 ml (c″ ) Trimethylolethane 10g (d″) 10% ethanol solution of guanidine trichloroacetic acid 10ml (e″) 10% polyvinylpyrrolidone aqueous solution 30ml (f″) Hardener 3% aqueous solution 5ml (g″) Gelatin 2g (h″) Water After mixing 20 ml or more of (a″) to (h″) and heating and melting, apply it on a subbed polyethylene terephthalate film so that the silver amount is 1.3 g/m ² and heat it. A developed color photosensitive material A-3 was produced. After imagewise exposing this photosensitive material A-3 to tungsten light through a sensitometric light wedge,
15 seconds after the start of heating, the entire surface was exposed for 10 seconds at an exposure intensity of 250 lux using tungsten light as a light source, and then for 40 seconds on a heat block at 150 lux.
The mixture was heated uniformly to ℃. Next, styrene and N-benzyl
The image-receiving material coated with an image-receiving layer consisting of a 1:1 copolymer of N,N-dimethyl-N-(3-maleimidopropyl)ammonium chloride and acid-treated gelatin is immersed in water, and then subjected to the above-mentioned full-surface exposure. The film was placed on top of the heat-developable photosensitive material so that the film surfaces were in contact with each other. After 30 seconds, the image-receiving material was peeled off from the photosensitive material, and a positive magenta transferred image was obtained on the image-receiving material. The reflection density of this positive image was measured using the densitometer, and the maximum density was 1.56 and the minimum density was 0.62. [Preparation of heat-developable photosensitive material A-4] 0.4 g of 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone and polyethylene were added to the photosensitive coating solution A-3 of the heat-developable photosensitive material A-3 as a reducing agent. A heat-developable color photosensitive material A-4 was prepared in exactly the same manner as Sample A-3 except that 2 g of glycol was added. This photosensitive material A-4 was subjected to the same operations and treatments as Sample A-3. The resulting magenta transfer color image has a maximum reflection density of 1.71 and a minimum density of 0.47.
It was hot. Example 3 A laminated multicolor photothermographic material was prepared by sequentially coating the layers described below on a 150 μm thick transparent polyethylene terephthalate support coated with an undercoat. (1) Red-sensitive internal latent image type silver chlorobromide emulsion layer Red-sensitized emulsion of internal latent image type silver chlorobromide grains prepared in Example-1 (silver coating amount 2.0 g/m ² ), 4-
Sulfobenzotriazole silver (silver coating amount 0.5g/
m ² ), the cyan image-providing substance C-1 (0.7 g/
^m2 ), 3-methyl-1,3,5-pentanetriol (1.2g/ ^m2 ), sodium 4-(diethylamino)-2methylsulfamate (0.5g/ ^m2 ), gelatin (1.2g/m2), m ² ) and polyvinylpyrrolidone (1.2
( ² ) Intermediate layer A layer consisting of gelatin (0.4 g/m ² ) and polyvinylpyrrolidone (0.4 g/m ² ) (3) Green-sensitive internal latent image type silver chlorobromide emulsion layer Green Sensitized internal latent image type silver chlorobromide emulsion (1.7
g/m ² ), 4-sulfobenzotriazole silver (silver coating amount 0.5 g/m ² ), the magenta dye-providing substance M
-1 (0.7g/m ² ), 3-methyl 1,3,5-pentanetriol (1.2g/m ² ), 4-(diethylamino)-2methylphenylsulfamic acid sodium (0.5g/m ² ) , layer (4) consisting of gelatin (1.2 g/m ² ) and polyvinylpyrrolidone (1.2 g/m ² ), middle layer layer (5) consisting of gelatin (0.4 g/m ² ) and polyvinylpyrrolidone (0.4 g/m ² ) ) Blue-sensitive internal latent image type silver chlorobromide emulsion layer Blue-sensitized internal latent image type silver chlorobromide emulsion (2.0
g/m ² ), 4-sulfobenzotriazole silver (silver coating amount 0.5 g/m ² ), the yellow dye-donor Y
-1 (0.8 g/m ² ), 3-methyl 1,3,5-pentanetriol (1.2 g/m ² ), 4-(diethylamino)-2-methylphenylsulfamic acid sodium (0.6 g/m ^{2 )} ), gelatin (1.2 g/m ² ) and polyvinylpyrrolidone (1.2 g/m ² ) (6) Intermediate layer A compound having the following structure (0.6 g/m ² ) and gelatin (0.4 g/m ² ) and Layer made of polyvinylpyrrolidone (0.4g/m ² ) (7) Protective layer Layer consisting of gelatin (0.3 g/m ² ) and glyoxal (0.03 g/m ² ) After the photothermographic material obtained above is imaged with tungsten light through a sensitometry light wedge. After heating for 10 seconds on a heat block heated to 150°C, the entire surface was exposed to light for 10 seconds at an exposure intensity of 100 lux using tungsten light as a light source, and then returned to room temperature. Next, the thermal transfer image-receiving material used in Example 1 and the above-mentioned exposed photothermographic material were superimposed so that their film surfaces were in contact with each other, and heat development was performed at 150° C. for 1 minute in a heat developing device. Thereafter, the image-receiving material was immediately peeled off to obtain a color image diffusely transferred onto the image-receiving material. The maximum density (Dmax) and minimum density (Dmin) of the obtained positive image were measured using the densitometer, and the results are shown in Table 2.

[Table] As is clear from the results in Table 2, it can be seen that good dye positive images can be obtained even in the heat-developable color photosensitive material having a multilayer structure according to the present invention.

Claims (1)

[Claims] 1 After imagewise exposure of a silver halide photosensitive material having a silver halide emulsion layer containing at least a dye image-providing substance and internal latent image type silver halide whose surface has not been coupled in advance on a support, the material is substantially developed. a step of heating within a range that does not cause the formation of imagewise formation in the silver halide emulsion layer by the action of heating; or transferring the released dye to an image-receiving element.