JPH0560094B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an image forming method including a heating step, and more particularly, to an image forming method including a heating step containing a precursor of a photographically useful reagent. (Prior art) Photography using silver halide has been the most widely used method since it has excellent photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. I've been exposed to it. In recent years, a technology has been developed that allows images to be easily and quickly obtained by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developer to a dry processing using heating, etc. It has been. Heat-developable photosensitive materials are well known in the art, and for more information on heat-developable photosensitive materials and their processes, see, for example, Fundamentals of Photographic Engineering (published by Corona Publishing, 1979).
Pages 553-555, 40 pages of video information published in April 1978, Nebrez Handbook of Photography
And Reprography 7th Edition (Nebletts
Handbook of Photography and Reprography
7th) Ed. Van Norstrand Reinhold Company ((Van Norstrand Reinhold
Company), pages 32-33, US Pat. No. 3,152,904,
No. 3301678, No. 3392020, No. 3457075, British Patent No. 1131108, No. 1167777, and Research Disclosure Magazine (June 1978 issue, pages 9-15 (RD-17029)).Color For information on how to obtain images (color images),
Many methods have been proposed. Regarding the method of forming a color image by combining an oxidized developer and a coupler, U.S. Pat.
- Aminophenol-based reducing agent has been awarded a Belgian patent
Issue 802519 and Research Disclosure Magazine
September 1975, pages 31 and 32, proposes a sulfonamidophenolic reducing agent, and US Pat. No. 4,021,240 proposes a combination of a sulfonamidophenolic reducing agent and a 4-equivalent coupler. Furthermore, regarding the method of forming positive color images using the photosensitive silver dye bleaching method, see, for example, Research Disclosure Magazine, April 1976 issue, pages 30-32 (RD-14433), December 1976 issue, pages 14-15 of the same magazine. Page (RD-15227), U.S. Pat. No. 4,235,957, and others, useful dyes and bleaching methods are described. Furthermore, an image forming method by thermal development using a compound that has a dye moiety in advance and can release a mobile dye in response to or inversely to the reduction reaction of silver halide to silver at high temperatures has been patented in a European patent. Publication No.
No. 76492, No. 79056, JP-A-58-28928, No. 58
−26008. In addition, a method for transferring a mobile dye image-wise formed by heat development to an image-receiving layer by heating and an image-receiving material used therefor are disclosed in Japanese Patent Application Laid-Open No.
It is described in No. 58543, No. 58-79247, No. 59-168439, etc. However, in such an image forming method that includes a heating step, it is impossible to expect the necessary photographic reagents to be supplied from the developer, etc., so all the photographic reagents necessary for development must be built into the photosensitive material in advance. There is. However, if a photographic reagent is added to a photosensitive material in an active form, it may react with other components in the photographic material during storage before processing or decompose due to the influence of heat, oxygen, etc. , the expected performance cannot be achieved during processing. One method for solving these problems is to block the active groups of the photographic reagent and add it to the photographic light-sensitive material in a substantially inactive form, that is, as a photographic reagent precursor. When a useful photographic reagent is a dye, blocking the functional groups that greatly affect the spectral absorption of the dye and shifting the spectral absorption toward shorter or longer wavelengths allows for the removal of halogens with corresponding photosensitive spectral regions. Even if it coexists in the same layer as the silver oxide emulsion layer, it has the advantage that sensitivity does not decrease due to the so-called filter effect. If a useful photographic reagent is an antifoggant or a development inhibitor, by blocking the active groups, it is possible to suppress the desensitizing effect by adsorption to photosensitive silver halide during storage and the formation of silver salts, and at the same time suppress the desensitization effect when necessary. By releasing these photographic reagents at appropriate timings, there are advantages such as reducing fog without impairing sensitivity, suppressing overdevelopment fog, or stopping development at a required time.
When useful photographic reagents are developing agents, auxiliary developers, or fogging agents, blocking the active or adsorbent groups prevents various adverse photographic effects due to the formation of semiquinones and oxidants due to air oxidation during storage. Another advantage is that fog nucleation during storage can be prevented by preventing electron injection into silver halide, and as a result, stable processing can be realized. Even if the photographic reagent is a bleaching accelerator or a bleaching/fixing accelerator, by blocking the active groups, it is possible to suppress reactions with other components contained therein during storage, and to remove the blocking groups during processing. This has the advantage that the desired performance can be achieved at the required time. Regarding such photographic reagent blocking techniques, some specific techniques are already known in conventional conventional photographic materials. For example, those using blocking groups such as acyl groups and sulfonyl groups described in Japanese Patent Publication No. 47-44805, Japanese Patent Publication Nos. 54-17369 and 55-
Nos. 9696 and 55-34927, which utilize a blocking group that releases a photographic reagent through the so-called reverse Michael reaction; , 57-136640
A blocking group that releases a photographic reagent upon the production of quinone methide or a quinone methide-like compound through intramolecular electron transfer, as described in the specification;
Those utilizing the intramolecular ring-closing reaction described in JP-A-55-53330, or JP-A-57-76541
Known techniques include those that utilize 5- or 6-membered ring cleavage as described in No. 57-135949 and No. 57-179842. However, all of these known techniques reduce OH ^- during wet development.
It utilizes hydrolysis or deprotonation due to the action of , and precursor technology for dry treatment using an organic base is not yet known. (Objective of the Invention) Therefore, the object of the present invention is to provide a precursor technology for a photographically useful reagent in an image forming method having a heating step, which is stable at room temperature and is stable during thermal development or mobile dyes. An object of the present invention is to provide a compound having the function of releasing a photographically useful reagent for the first time upon thermal transfer. Another object of the present invention is to provide an image forming method having a heating step that hardly causes image unevenness even if there are variations in development temperature or transfer temperature. (Disclosure of the Invention) The above objects of the present invention have been achieved by a dry image forming method characterized by heating in the presence of a compound represented by the following general formula (). In the formula, X represents a carbon atom necessary to complete a benzene ring or a naphthalene ring, and R is a group that can be converted into a hydroxyl group or a dissociated product thereof in a heating step, and is a group that can be converted into a hydroxyl group or a dissociated product thereof in the heating process, and is a group that can be converted into a hydroxyl group or a dissociated product thereof in the heating step, and is a group such as (A), (B), Represents a group selected from (C). Q represents an aryl group or a substituted aryl group. Also, Q is

[Formula] May be bonded to TIME or PUG directly or via another atom. TIME represents a timing base. PUG stands for photographic useful group. n represents 0 or an integer. Furthermore, the present invention will be explained in further detail. X represents a carbon atom group necessary to complete a benzene ring or a naphthalene ring, but a carbon atom group necessary to complete a benzene ring is more preferred. In the case of benzene ring,

[Formula] is preferably present at the ortho or para position relative to R. Further, the carbon atoms forming this benzene ring or naphthalene ring may be substituted with a suitable substituent other than hydrogen atom. Examples of permissible substituents for the benzene ring or naphthalene ring include halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, alkoxy groups, aryloxy groups, acylamino groups,
alinino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group,
Examples include alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imido group, heterothio, sulfinyl group, phosphonyl group, aryloxycarbonyl group, and acyl group. R represents a group that can be converted into a hydroxyl group (or a dissociated product thereof) during thermal development or thermal transfer, and preferred examples include the following (A), (B) and (C). However, R ¹¹ and R ¹² may be the same or different, and each is a substituted or unsubstituted alkyl group, a cycloalkyl group, a substituted or unsubstituted alkenyl group, an aralkyl group, a substituted or unsubstituted aryl group. represents a group selected from a group, a heterocyclic residue, an alkylthio or aryloxy group, an alkylthio or arylthio group, and a substituted or unsubstituted amino group. Furthermore, R ¹¹ and R ¹² may be combined with each other to form a 5- or 6-membered ring. The alkyl group allowed for R ¹¹ and R ¹² is preferably a straight chain or branched alkyl group having 1 to 18 carbon atoms, specifically a methyl group, ethyl group, n-propyl group, n-butyl group. , n-hexyl group, n-heptyl group, 2-ethylhexyl group,
Examples include n-decyl group and n-dodecyl group. Substituents for substituted alkyl groups include halogen atoms, alkoxy groups, aryloxy groups, cyano groups, alkyl or arylthio groups, substituted or unsubstituted carbamoyl groups, alkyl or arylsulfonyl groups, alkyl groups or aryl groups substituted with Examples include a disubstituted amino group, a hydroxyl group, a carboxy group, a sulfo group, an acylamino group, and a sulfonylamino group. The cycloalkyl group has 5 to 10 carbon atoms.
to 6-membered cycloalkyl groups are preferred, and specific examples include cyclopentyl and cyclohexyl groups. Examples of the alkenyl group include a vinyl group, an allyl group, a crotyl group, and a substituted or unsubstituted styryl group. Examples of aralkyl groups include benzyl group, β-
Examples include phenethyl group. As the aryl group, an aryl group having 6 to 18 carbon atoms is preferable, and specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, and the like. Substituted aryl groups include substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, halogen atoms, acylamino groups, sulfonylamino groups, cyano groups, nitro groups, and alkyl groups. or an arylthio group, an alkyl or arylsulfonyl group, a carbonyloxy group, a hydroxy-substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a disubstituted amino group substituted with an alkyl group or an aryl group, a carboxy group, a sulfo group , an alkyl or aryloxycarbonyl group, and the like. The heterocyclic residue is preferably a 5- or 6-membered heterocycle containing oxygen, nitrogen, or sulfur as a heteroatom, examples of which include pyridyl, furyl, thienyl, pyrrole, indolyl, and the like. Further, this heterocyclic residue may have a substituent shown as an example of the substituent for the above-mentioned substituted aryl group. Preferred examples of the alkyloxy or aryloxy group and the alkylthio or arylthio group are represented by (D) and (E) below. −OR ¹³ (D) −SR ¹⁴ (E) As a preferable example of R ¹³ and R ¹⁴ , R ¹¹ and
Examples of the alkyl group and aryl group listed in the section of R ¹² may be mentioned. Also R ¹³ and
R ¹⁴ may have any of the permissible substituents for R ¹¹ and R ¹² . Among (A), (B), and (C), (A) is preferable, and (A)
It is also preferred that R ¹¹ be an aryl group or a substituted aryl group. Q represents an aryl group or a substituted aryl group, and preferable examples thereof include R ¹¹ and R ¹²
Examples are similar to those given in the section. Also, Q is

[Formula] may be bonded to TIME or PUG directly or via another atom. TIME represents a so-called timing group. Typical examples include JP Publication No. 55-9696, JP No. 58-Sho.
1139, as described in the specifications of No. 58-1140, etc.

[Formula] group, or the -OCH ₂ -(PUG) group described in JP-A No. 59-93442. Photographically useful reagents (PUGs) released from precursor compounds include, for example, antifoggants,
Development inhibitor, developer, development accelerator, electron donor (ED), fogging agent, nucleating agent, silver halide solvent, bleaching accelerator, bleaching/fixing accelerator, fixing accelerator, dye, for color diffusion transfer Examples include coloring materials, couplers, melting point depressants for heat-sensitive materials, and coupling inhibitors for diazothermographic materials. Specific examples of antifoggants and development inhibitors include nitrogen-containing heterocyclic compounds having a mercapto group.
As developing agents and development accelerators, hydroquinones, catechols, aminophenols, p-
Examples include phenylene diamines, pyrazolidones, and ascorbic acids. electron donor, fogging agent,
Nucleating agents include α-hydroxyketones, α-
These include sulfonamide ketones, hydrazines, hydrazides, tetrazolium salts, aldehydes, acetylenes, quaternary salts, and isodos. Examples of silver halide solvents include thioethers, rhodanines, hypo, methylene bissulfones, and the like.
Bleaching accelerators and bleaching/fixing accelerators include aminoethanethiols, sulfoethanethiols, aminoethanethiocarbamates, and the like.
Hypo is an example of a fixing accelerator. Examples of dyes include azo dyes, azomethine dyes, anthraquinone dyes, and indophenol dyes. Among the above-mentioned photographically useful groups, development inhibitors exhibit particularly remarkable effects when blocked in the form of the general formula ().Among them, the inhibitors with particularly large effects are represented by the following general formula (). It can be done. However, Y represents an atomic group necessary to form a 5- or 6-membered heterocycle (preferably one containing a sulfur atom, a nitrogen atom, or an oxygen atom in the ring). In the general formula (), the blocking group is bonded at the sulfur or nitrogen atom. Preferred examples of the development inhibitor represented by the general formula () include the following compounds.

【formula】

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【formula】 【formula】

Here, R ¹⁶ represents a group selected from a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group, and an aralkyl group, and these groups may have an appropriate substituent, Typical examples include the permissible substituents for R ¹¹ . Further, the carbon atoms forming the above ring structure may be substituted with other substituents other than hydrogen atoms,
Typical examples thereof are the permissible substituents on the benzene or naphthalene rings mentioned above. It is well known that a nitrogen-containing heterocyclic compound having a mercapto group represented by () has a development inhibiting effect in silver halide photosensitive materials, and it is also used in heat developable photosensitive materials, for example, in Japanese Patent Application No. 176351/1989.
There is a description in . However, if, for example, a compound represented by formula () is added to the emulsion layer from the beginning, development is suppressed from the initial stage of development, resulting in a decrease in image density and low sensitivity. However, since the compound represented by the formula () of the present invention gradually releases the development inhibitor () during thermal development, development can be stopped without reducing image density. Furthermore, by incorporating the compound of the present invention (2) in which the development inhibitor (2) is blocked, a heat-developable photosensitive material or a dye-fixing material having the ability to compensate for temperature unevenness in development temperature or transfer temperature can be obtained. Since development is usually carried out at a high temperature of over 100°C, slight temperature unevenness is unavoidable. Since the image density is high in higher temperature areas and lower in lower temperature areas, unevenness in the image as a whole, especially in non-image areas, does not occur.
Furthermore, development may proceed during heat transfer of the movable raw dye, and if fog increases or heating temperature is uneven, unevenness may occur in the transferred image density. However, when the compound () of the present invention is contained, a large amount of the development inhibitor () is released in higher temperature areas, and the achieved image density is suppressed, resulting in uneven image density and fogging during heat transfer as a whole. succeeded in reducing it. In the compound () of the present invention, when R is converted into a hydroxyl group (or its dissociated product) by the action of a nucleophile during thermal development or heat transfer, and PUG (or its dissociated product) is further released by intramolecular electron transfer. It is thought that quinone methide () is formed at the same time. In the general formula (), -R is

An example in which a compound of the formula [formula] and Q is a hydrogen atom is hydrolyzed in an aqueous alkaline medium to form a phenol, and further forms a quinone methide while releasing a photographic reagent is disclosed in US Pat. No. 3,674,478, etc. It is described in. However, even in an image forming method that includes a heating step that does not contain water or alkali due to dry processing, development inhibitory substances are efficiently released from the compound () during thermal development or thermal transfer. This is the first time this has been discovered. This was a completely unexpected result based on the above materials. Furthermore, we have now found that by introducing an aryl group or a substituted aryl group to Q, the release rate of (PUG) is accelerated compared to the above-mentioned compound in which Q is a hydrogen atom. This is considered to be because the produced quinone methide () is stabilized by introducing an aryl group or a substituted aryl group to Q. That is, we succeeded in increasing the release efficiency of (PUG) from ( ) formed during thermal development or thermal transfer, and as a result, we succeeded in more effectively expressing the development suppressing effect. (A), (B), which were discovered this time as preferable examples of R
In order to regenerate the hydroxyl group from (C), it is generally necessary to assume attack by some kind of nucleophile. Although the content of this nucleophile is not clear, for example, various terminal residues of amino acids (-NH ₂ , -OH, -
CO ₂ H, −SH,

[Formula] etc.) can be assumed. The reaction between these terminal residues and the compound () is extremely slow at room temperature, but in the image forming method of the present invention, it is accelerated due to the high temperature treatment.
It is thought that the release of PUG became possible. Furthermore, when a base or a base precursor is used as a development accelerator, the base acts as a nucleophile upon heating and promotes the release of PUG. For this reason,
The combination of bases or base precursors with the compounds of the invention () is particularly advantageous. Furthermore, although it can be expected that the reaction between the compound of the present invention represented by the formula () and the nucleophilic reagent occurs in a solution, a similar reaction is effective in a short period of time even in a dry film and upon heating. This was an unexpected discovery. Specific examples of the present invention are shown below, but the present invention is not limited thereto. (1) (2) (3) (Four) (Five) (6) (7) (8) (9) (Ten) (11) (12) (R) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (twenty three) (twenty four) (twenty five) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36) (37) (38) (39) (40) (41) (42) (43) (44) (45) (46) (47) (48) (49) (50) (51) (52) (53) (54) Next, the synthesis method of the present invention will be described. The compound () of the present invention (provided that X forms a benzene ring and n is 0) is the corresponding halide
It can be synthesized by a substitution reaction between (V) and (PUG). (However, X represents a halogen atom) The halide (V) used here can be easily synthesized by either method (b) or (c) below. The alcohol () can be synthesized by reducing the corresponding ketone (d) or by reacting an aldehyde with a Grignard reagent (e). (However, X represents a halogen atom.) For the substitution reaction (a), it is preferable to use an organic base such as triethylamine or an inorganic base such as potassium carbonate. Furthermore, if the sodium salt of thiol is prepared in advance and used, the reaction proceeds smoothly. Side chain halogenation in (b) includes chlorine, sulfuryl chloride, bromine, N-chlorosuccinimide, N-
This is carried out using bromosuccinimide or the like. In this case, it is preferable to use a radical initiator such as benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN), and light irradiation is often effective. For the halogenation of alcohol in (c), it is preferable to use hydrogen chloride, thionyl chloride, hydrogen bromide, or the like. A synthesis example is given below. Synthesis example Synthesis of compound (11) Synthesis of Compound (11)-a An acetonitrile solution of 27.2 g (0.2 mol) of p-benzylphenol and 29.3 ml (0.21 mol) of triethylamine was cooled and stirred to below 10°C, and while maintaining this temperature, 29.5 g of p-chlorobenzoic acid chloride was added. g
(0.21 mol) was added dropwise. After the reaction was completed, the reaction was carried out at room temperature for 30 minutes, and the reaction product was added to water, and the precipitate was extracted with ethyl acetate. After drying over sodium sulfate, ethyl acetate was distilled off under reduced pressure, 300 ml of n-hexane was added to the residue, and the precipitated crystals were collected to give 47.8 g of compound (11)-a.
(0.148 mol) was obtained. Yield 74% Synthesis of compound (11)-b Carbon tetrachloride solution containing 39 g (0.12 mol) of compound (11)-a, 21 g (0.118 mol) of N-bromosuccinimide, and a trace amount of benzoyl peroxide as a radical initiator. 300 ml was refluxed for 1 hour while irradiated with light. After completion of the reaction, the precipitated succinimide crystals were heated, and when the mother liquor was cooled, new crystals were precipitated. After cooling to 18°C, the precipitated crystals were collected and washed with carbon tetrachloride to give 35.5 g of compound (11)-b (0.0884
mole) was obtained. Yield 74% Synthesis of compound (11) Compound (11)-b 16 g (0.04 mol), 2-mercaptobenzimidazole-5-sulfonamide 8.2 g
(0.036 mol), anhydrous potassium carbonate 5.5 g (0.04 mol)
160 ml of an acetone solution was stirred under reflux for 2 hours. After cooling with water, remove the precipitate and wash with acetone, then remove and wash thoroughly with water to remove inorganic salts and form compound (11).
12.5 g (0.0227 mol) was obtained. Yield 63% Melting point
179-181°C The amount of the compound of the present invention to be used varies depending on the compound and the system used, but it is generally 50% by weight or less when calculated by weight of the coating film, and is preferably 50% by weight or less. In the range of 30% by weight or less. The optimum amount used depends in particular on the structure of the development inhibitor () released. Furthermore, the above-mentioned development inhibiting substances () include compounds that have the property of promoting development in small amounts and inhibiting development in increasing amounts. Therefore, the addition of the compound () of the present invention that releases such a compound () is particularly advantageous because early development is promoted and late development is suppressed. The compound of the present invention can be dissolved in a water-soluble organic solvent (for example, methanol, ethanol, acetone, dimethylformamide) or a mixed solution of this organic solvent and water, and then incorporated into the binder. The hydrophobic compound of the present invention can also be made into fine particles and contained in the binder by an oil protection method. Moreover, the compounds of the present invention can be used alone or in combination of two or more. Furthermore, it is also possible to use a development stopper or a development stop technique other than the one of the present invention. These development stoppers and development stop technologies were developed in a patent application filed in 1983.
-216928, a method using thermal decomposition of aldoxime esters described in Japanese Patent Application No. 59-48305,
Known methods include a method using Lotusene rearrangement described in Japanese Patent Application No. 59-85834, and a method using a carboxylic acid ester described in Japanese Patent Application No. 59-85836. In the present invention, an image forming method having a heating step only needs to include a heating step in any of the image forming processes, and it does not matter whether it is heating for development or heating for transfer. do not have. Alternatively, it may be heated in an imagewise manner. As heat-developable photosensitive materials used in image forming methods that involve heating for development, there are those using silver halide and those using diazo compounds. The compound of the present invention may be added to these light-sensitive materials, or when an image-receiving layer is provided on a separate support, it may be added to any layer on this support. Alternatively, it may be supplied from outside during heating. In the present invention, the image forming method having a heating step is a material known as a so-called heat-developable photosensitive material (for example, a material described in the above-mentioned prior art).
It is preferable to use That is, the compound represented by the general formula () is added to any layer (for example, a photosensitive layer,
It may be included in an intermediate layer, a protective layer), or it may be added to a material that fixes a mobile dye distributed in an image (dye fixing material). It is also preferable that the photothermographic material uses silver halide as a photoreceptor. Appropriate heating temperature is about 50°C to about 250°C, and particularly useful is 60°C to 180°C. Silver halides that can be used in the present invention include silver chloride,
Silver bromide, silver iodide, or silver chlorobromide, silver chloroiodide,
Either iodobromide salt or silver chloroiodobromide may be used. The halogen composition within the particles may be uniform, or may have a multiple structure with different compositions on the surface and inside (Japanese Patent Application Laid-open No. 154232/1983, 108533/1983, 59/1982).
No. 48755, No. 59-52237, US Pat. No. 4,433,048 and European Patent No. 100,948). In addition, tabular grains with a grain thickness of 0.5 μm or less, a diameter of at least 0.6 μm, and an average aspect ratio of 5 or more (U.S. Pat.
4414310, OLS No. 4435499, OLS No. 3241646A1, etc.), or monodispersed emulsions with a nearly uniform grain size distribution (JP-A-57-178235).
No. 58-100846, No. 58-14829, International Publication
83/02338A1, European Patent No. 64412A3 and
83377A1 etc.) can also be used in the present invention. Two or more types of silver halides having different crystal habit, halogen composition, grain size, grain size distribution, etc. may be used in combination. The gradation can also be adjusted by mixing two or more types of monodispersed emulsions with different grain sizes. The average grain size of the silver halide used in the present invention is preferably from 0.001 μm to 10 μm, more preferably from 0.001 μm to 5 μm. These silver halide emulsions may be prepared by any of the acid method, neutral method, or ammonia method, and the reaction method of the soluble silver salt and soluble halide salt may be one-sided mixing method, simultaneous mixing method, or any of these methods. Any combination of these may be used. A back-mixing method in which particles are formed in excess of silver ions or a controlled double-jet method in which pAg is kept constant can also be used. Furthermore, in order to accelerate grain growth, the concentration, amount, or rate of addition of silver salts and halogen salts may be increased (Japanese Patent Application Laid-open No. 142329/1983,
No. 55-158124, U.S. Patent No. 3650757, etc.). Epitaxial junction type silver halide grains can also be used (JP-A-56-16124, US Pat. No. 4,094,684). In the present invention, when silver halide is used alone without an organic silver salt oxidizing agent, X
Silver chloroiodide, silver iodobromide, which has a line pattern,
Preference is given to using silver chloroiodobromide. For example, silver bromide grains are prepared by adding a silver nitrate solution to a potassium bromide solution, and by further adding potassium iodide, silver iodobromide having the above characteristics can be obtained. In the step of forming silver halide grains used in the present invention, ammonia,
Organic thioether derivatives described in Japanese Patent Publication No. 47-11386 or sulfur-containing compounds described in Japanese Patent Publication No. 53-144319 can be used. In the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be present. Further, for the purpose of improving high illuminance failure and low illuminance failure, water-soluble iridium salts such as iridium chloride (2) and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used. The soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening, and thus the Nudel water washing method or the precipitation method can be applied. Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-open No. 1986-1999).
126526, 58-215644). The silver halide emulsion used in the present invention may be of the surface latent image type in which latent images are mainly formed on the grain surfaces, or may be of the internal latent image type in which the latent images are formed inside the grains. Direct reversal emulsions combining internal latent image emulsions and image nucleating agents can also be used. Internal latent image emulsions suitable for this purpose are disclosed in U.S. Pat. No. 2,592,250;
No. 3761276, Special Publication No. 58-3534 and Japanese Patent Publication No. 3761276
It is described in No. 57-136641, etc. Preferred nucleating agents for combination in the present invention include US Pat.
No. 3227552, No. 4245037, No. 4255511, No. 4266031, No. 4276364 and OLS No.
It is described in No. 2635316 etc. The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g/m ² in terms of silver. In the present invention, an organic metal salt that is relatively stable to light can be used together with the photosensitive silver halide as an oxidizing agent. In this case, the photosensitive silver halide and the organic metal salt need to be in contact or at a close distance. Among such organic metal salts, organic silver salts are particularly preferably used. When an organic metal salt is used in combination, the temperature of the heat-developable photosensitive material is 80°C or higher, preferably 100°C.
When heated to a temperature of .degree. C. or higher, the organometallic oxidizing agent is also considered to participate in redox using the silver halide latent image as a catalyst. Examples of organic compounds that can be used to form the organic silver salt oxidizing agent include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds. Can be mentioned. Silver salts of aliphatic carboxylic acids include behenic acid,
Stearic acid, oleic acid, lauric acid, capric acid, myristic acid, palmitic acid, maleic acid, fumaric acid, tartaric acid, furoic acid, linoleic acid, linolenic acid, oleic acid, adipic acid, sebacic acid, succinic acid, acetic acid, butyric acid , or silver salts derived from camphoric acid. Silver salts derived from these fatty acids substituted with halogen atoms or hydroxyl groups, or aliphatic carboxylic acids having thioether groups can also be used. Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include benzoic acid, 3,5
-dihydroxybenzoic acid, o-, m- or p
-methylbenzoic acid, 2,4-dichlorobenzoic acid,
acetamidobenzoic acid, p-phenylbenzoic acid,
Gallic acid, tannic acid, phthalic acid, terephthalic acid, salicylic acid, phenylacetic acid, pyromellitic acid or 3-carboxymethyl-4-methyl-4-
Representative examples include silver salts derived from thiazoline-2-thione and the like. As a silver salt of a compound having a mercapto or thiocarbonyl group, 3-mercapto-4-phenyl-1,2,4
- dithiocarboxylic acids such as triazole, 2-mercaptobenzimidazole, 2-mercapto-5-aminothiadiazole, 2-mercaptobenzothiazole, S-alkylthioglycolic acid (alkyl group has 12 to 22 carbon atoms), dithioacetic acid,
Thioamides such as thiostearamide, 5-carboxy-1-methyl-2-phenyl-4-thiopyridine, mercaptotriazine, 2-mercaptobenzoxazole, mercaptooxadiazole or 3-amino-5-benzylthio-1,
Examples include silver salts derived from mercapto compounds such as 2,4-triazole described in US Pat. No. 4,123,274. Examples of the silver salt of a compound having an imino group include benzotriazoles or derivatives thereof described in Japanese Patent Publication No. 44-30270 or 45-18416, such as benzotriazole, alkyl-substituted benzotriazoles such as methylbenzotriazole, and 5-chlorobenzotriazole. halogen-substituted benzotriazoles such as butylcarboimitobenzotriazole, nitrobenzotriazoles described in JP-A-58-118639, sulfobenzotriazole and carboxybenzotriazole as described in JP-A-58-118638. or a salt thereof, or hydroxybenzotriazole, etc., 1,2,4- as described in US Pat. No. 4,220,709.
Typical examples include silver salts derived from triazole, 1H-tetrazole, carbazole, saccharin, imidazole, and derivatives thereof. In addition, organic metal salts other than silver salts such as silver salts and copper stearate described in RD17029 (June 1978), and carboxylic acids having an alkynyl group such as phenylpropiolic acid described in Japanese Patent Application No. 1982-221535. Silver salts of can also be used in the present invention. The above organic silver salts can be used together in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of photosensitive silver halide. The total coating amount of photosensitive silver halide and organic silver salt is 50 mg to 10
g/m ² is suitable. The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments,
Holopolar cyanine dye, hemicyanine dye,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat.
2933390, US Pat. No. 3635721, etc.), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,743,510, etc.), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3615613, U.S. Patent No. 3615641, U.S. Patent No.
The combinations described in No. 3617295 and No. 3635721 are particularly useful. In order to incorporate these sensitizing dyes into a silver halide photographic emulsion, they may be directly dispersed in the emulsion, or they may be dispersed in a solvent such as water, methanol, ethanol, acetone, methyl cellosolve, etc. alone or in a mixture. It may be dissolved in a solvent and added to the emulsion. Alternatively, they may be dissolved in a substantially water-immiscible solvent such as phenoxyethanol, then dispersed in water or a hydrophilic colloid, and this dispersion may be added to the emulsion. Furthermore, these sensitizing dyes can be mixed with a lipophilic compound such as a dye-donating compound and added at the same time. Further, when dissolving these sensitizing dyes, the sensitizing dyes used in combination may be dissolved separately, or a mixture may be dissolved. When added to an emulsion, they may be added simultaneously as a mixture, separately, or simultaneously with other additives. It may be added to the emulsion at or before chemical ripening, or before or after nucleation of silver halide grains according to US Pat. No. 4,183,756 and US Pat. No. 4,225,666. The amount added is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide. In the present invention, when photosensitive silver halide is reduced to silver under high temperature conditions, a compound that generates or releases a mobile dye in response to or inversely to this reaction, i.e., a dye-donating compound, is used. It is preferable that the substance contains a sexual substance. Next, the dye-donating substance will be explained. Examples of dye-donating substances that can be used in the present invention include couplers that can react with a developer. In this method using couplers, the oxidized form of the developer produced by the redox reaction between the silver salt and the developer reacts with the coupler to form a dye, and is described in numerous documents. . Specific examples of developers and couplers include, for example, T.H. James The Theory.
Of the Photographic Process Part 4
Edition (by TH James, “The theory of the
"Photographic Process" 4th).Ed., pages 291-334 and 354-361, Shinichi Kikuchi, "Photographic Chemistry" 4th edition (Kyoritsu Shuppan), pages 284-295, etc. Dye-silver compounds in which a silver salt and a dye are combined can also be cited as examples of dye-donating substances.Specific examples of dye-silver compounds can be found in Research Disclosure Magazine, May 1978 issue, pages 54-58, (RD-
16966) etc. Furthermore, azo dyes used in heat-developable silver dye bleaching methods can also be cited as examples of dye-donating substances.
Specific examples of azo dyes and bleaching methods are disclosed in U.S. Patent No.
No. 4235957, Research Disclosure Magazine,
It is described in the April 1976 issue, pages 30-32 (RD-14433), etc. Further, leuco dyes described in US Pat. No. 3,985,565, US Pat. No. 4,022,617, etc. can also be cited as examples of dye-donating substances. Further, as another example of a particularly preferable dye-donating substance for the present invention, there may be mentioned, for example, a compound having the function of releasing or diffusing a diffusible dye in an imagewise manner, which is used in the method described in European Patent No. 76492. I can do it. This type of compound can be represented by the following general formula [L]. (Dye-X) _o -Y [L] Dye represents a dye group or a dye precursor group,
represents a simple bond or linking group, and Y corresponds to or inversely corresponds to a photosensitive silver salt having a latent image in the form of an image ( _Dye -X). , or represents a group having the property of releasing Dye and causing a difference in diffusivity between the released Dye and (Dye-X) _o -Y, where n represents 1 or 2, and n When is 2,
The two Dye-Xs may be the same or different. As a specific example of the dye-donating substance represented by the general formula [L], for example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in U.S. Pat. ,
It is described in the same No. 3544545, the same No. 3482972, etc. In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction has been published in Japanese Patent Application Laid-Open No. 51-63618, etc.
A substance that releases a diffusible dye through an intramolecular rewinding reaction of the isoxazolone ring was disclosed in JP-A-49-
It is described in No. 111628 etc. In all of these methods, the diffusible dye is released or diffused in areas where no development has occurred, and the dye is neither released nor diffused in areas where development has occurred. Furthermore, in these methods, development and dye release or diffusion occur in parallel, so it is very difficult to obtain an image with a high S/N ratio. Therefore, in order to improve this drawback, the dye-releasing compound is made into an oxidized form that does not have dye-releasing ability, and is made to coexist with a reducing agent or its precursor, and after development, it is reduced by the reducing agent that remains unoxidized. A method of releasing a diffusible dye has also been devised, and specific examples of the dye-donating substance used therein are disclosed in JP-A-53-110827 and JP-A-53-110827.
It is described in No. 54-130927, No. 56-164342, and No. 53-35533. On the other hand, as a substance that releases a diffusible dye in the area where development occurs, a substance that releases a diffusible dye through a reaction between a coupler having a diffusible dye as a leaving group and an oxidized developer is disclosed in British Patent No. 1330524. issue,
Special Publication No. 48-39165, U.S. Patent No. 3443940, etc.
Further, a substance that generates a diffusible dye through the reaction of a coupler having a diffusion-resistant group as a leaving group and an oxidized developer is described in US Pat. No. 3,227,550 and the like. In addition, in systems that use these color developers, image contamination due to oxidative decomposition products of the developer is a serious problem. Dye-releasing compounds have also been devised. Representative examples are shown below along with literature. Definitions in the general formula are described in each literature. U.S. Patent No. 3928312 etc. U.S. Patent No. 4053312 etc. U.S. Patent No. 4055428 etc. U.S. Patent No. 4,336,322 Japanese Patent Publication No. 59-65839 Japanese Patent Publication No. 59-69839 Japanese Patent Publication No. 53-3819 Japanese Patent Publication No. 51-104343 Japanese Patent Publication No. 51-104343 Japanese Patent Publication No. 51-104343 Research Disclosure Magazine No. 17465 US Patent No. 3725062 U.S. Patent No. 3728113 U.S. Patent No. 3443939 JP-A-58-116537 Any of the various dye-donating substances described above can be used in the present invention. Specific examples of imaging materials for use in the present invention are described in the patent documents cited above.
Since it is not possible to list all the preferred compounds here, some of them will be shown as examples. For example, the dye-providing substance represented by the general formula [L] can include the following. L-1 L-2 L-3 L-4 L-5 L-6 L-7 L-8 L-9 L-10 L-11 L-12 L-13 L-14 L-15 The compounds described above are just examples, and the invention is not limited thereto. In the present invention, the dye-donating substance is
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 2322027. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used. For example, phthanolic 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) ,
High boiling point organic solvents such as 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) , or boiling point of about 30℃
After dissolving in an organic solvent at 160°C, such as a lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, or cyclohexanone, it is hydrophilized. Dispersed into sex colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be used. In addition, various surfactants can be used when dispersing the dye-donating substance in the hydrophilic colloid, and these surfactants include those listed as surfactants elsewhere in this specification. You can use it. The amount of the high boiling point organic solvent used in the present invention is 10 g or less, preferably 5 g or less per 1 g of the dye-providing substance used. In the present invention, it is desirable to include a reducing substance in the light-sensitive material. Reducing substances include those generally known as reducing agents, as well as the aforementioned dye-donating substances having reducing properties. Also included are reducing agent precursors that do not themselves have reducing properties but develop reducing properties through the action of nucleophiles and heat during the development process. Examples of reducing agents used in the present invention include inorganic reducing agents such as sodium sulfite and sodium hydrogen sulfite, benzenesulfinic acids, hydroxylamines, hydrazines, hydrazides, borane-amine complexes, hydroquinones, and amino acids. In addition to phenols, catechols, p-phenylenediamines, 3-pyrazolidinones, hydroxytetrones, ascorbic acid, 4-amino-5-pyrazolones, etc. 4th edition (by TH James, “The
theory of the photographic process"4th),
Reducing agents described on pages 291 to 334 of Ed. can also be used.
Further, reducing agent precursors described in JP-A-56-138736, JP-A-57-40245, and US Pat. No. 4,330,617 can also be used. Combinations of various developers can also be used, such as those disclosed in US Pat. No. 3,039,869. In the present invention, the amount of the reducing agent added is 0.01 to 20 mol, particularly preferably 0.1 to 10 mol, per 1 mol of silver. Image formation accelerators can be used in the present invention. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of mobile dyes, and photosensitive material layers. It has functions such as promoting the movement of dye from the dye fixing layer to the dye fixing layer, and from a physicochemical function, it interacts with bases or base precursors, nucleophilic compounds, oils, hot solvents, surfactants, silver or silver ions. It is classified as a compound with However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Below, these image formation accelerators are classified by function and specific examples of each are shown. However, this classification is for convenience, and in reality, one compound may have multiple functions. many. (a) Base Examples of preferred bases include alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolates, metaborates as inorganic bases. ; ammonium hydroxide; hydroxide of quaternary alkylammonium; hydroxide of other metals, etc.; examples of organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines); ); aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted aromatic amines and bis[p-
(dialkylamino)phenyl]methanes), heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines, and those with a pKa of 8 or more are particularly preferred. (b) Base precursor Base precursors include salts of organic acids and bases that decompose by decarboxylation upon heating, and compounds that decompose and release amines through reactions such as intramolecular nucleophilic substitution reactions, Lothuzene rearrangement, and Beckman rearrangement. Those that cause some kind of reaction upon heating and release a base are preferably used. A preferred base precursor is British Patent No. 998949.
The salt of trichloroacetic acid described in U.S. Patent No.
α-sulfonylacetic acid salts described in No. 4060420;
Salts of propiolic acids described in JP-A No. 59-180573, 2-carboxycarboxamide derivatives described in U.S. Pat. No. 4,088,496, thermally decomposable products using an alkali metal or alkaline earth metal in addition to an organic base as the base component Salt with acid (patent application 1986-69597)
No.), Japanese Patent Application Laid-Open No. 1983-1987 using Lothsen rearrangement
Hydroxamic carbamates described in No. 168440, JP-A-59-1999, which produce nitriles by heating
Examples include aldoxime carbamates described in No. 157637. Others, UK Patent No. 998945
No., U.S. Patent No. 3220846, JP-A-50-22625
Also useful are the base precursors described in British Patent No. 2,079,480 and the like. (c) Nucleophilic compounds Water and water-releasing compounds, amines, amidines, guanidines, hydroxylamines, hydrazines, hydrazides, oximes, hydroxamic acids, sulfonamides, active methylene compounds, alcohols, thiols It is also possible to use salts or precursors of the above compounds. (d) Oil A high-boiling organic solvent (so-called plasticizer) used as a solvent when emulsifying and dispersing hydrophobic compounds can be used. (e) Thermal solvents Solid at ambient temperature, melts near the development temperature and acts as a solvent, such as ureas, urethanes, amides, pyridines, sulfonamides, sulfones, sulfoxides, esters,
Compounds such as ketones and ethers that are solid at temperatures below 40°C can be used. (f) Surfactant Pyridinium salts described in JP-A-59-74547;
Ammonium salts, phosphonium salts, JP-A-Sho
Examples include polyalkylene oxides described in No. 59-57231. (g) Compounds that interact with silver or silver ions Imides, nitrogen-containing heterocycles described in JP-A-59-177550, thiols, thioureas, and thioethers described in JP-A-59-111636. can be mentioned. The image formation accelerator may be incorporated into either the photosensitive material or the dye-fixing material, or may be incorporated into both. The layer to be incorporated may also be incorporated in the emulsion layer, intermediate layer, protective layer, dye fixing layer, and any layer adjacent thereto. The same applies to forms in which the photosensitive layer and the dye fixing layer are provided on the same support. The image formation accelerator can be used alone or in combination of several types, but generally a greater accelerating effect can be obtained when several types are used in combination. In particular, when a base or base precursor is used in combination with other promoters, a remarkable promoting effect is exhibited. Among the compounds of the present invention, a compound having a compound represented by the general formula () as a PUG is preferable because its effects are particularly exhibited when a base precursor is used. In that case, the ratio (molar ratio) of base precursor/compound of the present invention is preferably 1/20 to 20/1, more preferably 1/5 to 5/1. Further, in the present invention, it is possible to use a compound that activates the development and stabilizes the image at the same time.
Among them, isothiuroniums represented by 2-hydroxyethylisothiuronium trichloroacetate described in U.S. Patent No. 3301678, 1,8-(3,6-dioxaoctane)bis(isothiuronium・Bis(isothiuronium) such as trichloroacetate), thiol compounds described in West German Patent Publication No. 2162714,
Thiazolium compounds such as 2-amino-2-thiazolium trichloroacetate and 2-amine-5-bromoethyl-2-thiazolium trichloroacetate described in U.S. Pat. No. 4,012,260, bis(2-amino -2-
Thiazolium) methylenebis(sulfonylacetate), 2-amino-2-thiazolium phenylsulfonylacetate, 2-amino-2-thiazolium.2-carboxycarboxamide, and the like are preferably used. Furthermore, azole thioether and blocked azolinthion compounds described in Belgian Patent No. 768071, 4-aryl-1-carbamyl-2-tetrazoline-5-thione compounds described in U.S. Patent No. 3893859, and other U.S. Patent No. 3839041,
Compounds described in No. 3844788 and No. 3877940 are also preferably used. The binders used in the present invention can be contained alone or in combination. A hydrophilic binder can be used for this binder. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as proteins such as gelatin, gelatin derivatives, and cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, polyvinylpyrrolidone, Includes synthetic polymeric materials such as water-soluble polyvinyl compounds such as acrylamide polymers. Other synthetic polymeric materials include dispersed vinyl compounds, which increase the dimensional stability of photographic materials, especially in the form of latexes. The binder of the present invention is applied in an amount of 20 g or less per m ² , preferably 10 g or less, more preferably 7 g or less. The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is 1 c.c. of solvent or less, preferably 0.5 cc or less, more preferably 0.3 cc or less of solvent per 1 g of binder.
cc or less is appropriate. The photographic light-sensitive material and dye-fixing material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other binder layers. Examples include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), activated vinyl compound (1,3,
5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, 1,2-bis(vinylsulfonylacetamido)ethane, etc.), active halogen compounds (2,
(4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. The support used in the light-sensitive material and the dye-fixing material used in some cases in the present invention is one that can withstand processing temperatures. Common supports include glass, paper, metal and their analogs, as well as cellulose acetate film, cellulose ester film,
Included are polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film, and films or resin materials related thereto. Paper supports laminated with polymers such as polyethylene can also be used. US Patent No.
The polyesters described in No. 3634089 and No. 3725070 are preferably used. When using a dye-donating substance that releases an image-wise mobile dye in the present invention, a dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixing layer. In the method of supplying the dye transfer aid externally, water, caustic soda, caustic potash,
A basic aqueous solution containing an inorganic alkali metal salt is used. Further, a low boiling point solvent such as methanol, N,N-dimethylformamide, acetone, diisobutyl ketone, or a mixed solution of these low boiling point solvents and water or a basic aqueous solution is used. The dye transfer aid may be used in such a way that the image-receiving layer is wetted with the transfer aid. If the transfer aid is incorporated into the photosensitive material or dye fixing material, there is no need to supply the transfer aid from the outside.
The above transfer aid may be incorporated into the material in the form of crystal water or microcapsules, or may be incorporated as a precursor that releases the solvent at high temperatures. More preferably, a hydrophilic thermal solvent that is solid at room temperature and soluble at high temperature is incorporated into the light-sensitive material or dye-fixing material. The hydrophilic heat solvent may be incorporated into either the photosensitive material or the dye fixing material, or may be incorporated into both. Further, the layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto. Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. In the photosensitive material used in the present invention, in order to improve the sharpness of images, Japanese Patent Publication No. 48-3692,
U.S. Patent No. 3253921, U.S. Patent No. 2527583, U.S. Patent No.
Filter dyes, absorbent substances, etc. described in specifications such as No. 2956879 can be contained. In addition, these dyes are preferably thermally decolorizable, such as those disclosed in US Pat. No. 3,769,019 and US Pat.
Dyes such as those described in No. 3745009 and No. 3615432 are preferred. The photosensitive material used in the present invention may contain various additives known as heat-developable photosensitive materials and layers other than the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, an AH It can contain layers, release layers and the like. Various additives include those described in Research Disclosure Magazine Vol. 170, No. 17029, June 1978, such as plasticizers, sharpness improving dyes, AH dyes, sensitizing dyes,
Additives include matting agents, surfactants, optical brighteners, and anti-fading agents. The photographic element of the present invention is comprised of a light-sensitive element that forms or releases a dye upon heat development and, optionally, a dye-fixing element that fixes the dye. In particular, in systems that form images by diffusion transfer of dyes, a photosensitive element and a dye fixing element are essential, and in a typical form, the photosensitive element and dye fixing element are separately coated on two supports. It is broadly divided into two types: a form in which it is coated on the same support and a form in which it is coated on the same support. There are two types of forms in which the photosensitive element and the dye-fixing element are formed on separate supports: one is a peelable type and the other is a peelable type. In the case of the former peel-off type, after image exposure or heat development, the photosensitive element, the coated surface and the coated surface of the dye fixing element are overlapped, and after the transfer image is formed, the photosensitive element is immediately peeled off from the dye fixing element. Depending on whether the final image is of a reflective type or a transmissive type, the support of the dye fixing element can be selected as an opaque support or a transparent support.
Further, a white reflective layer may be coated if necessary.
In the case of the latter type that does not require peeling, it is necessary to have a white reflective layer interposed between the photosensitive layer in the photosensitive element and the dye fixing layer in the dye fixing element. It may be painted on any of the elements. The support of the dye fixing element needs to be a transparent support. A typical configuration in which the photosensitive element and the dye-fixing element are coated on the same support is a configuration in which there is no need to peel off the photosensitive element from the image-receiving element after the transfer image is formed. In this case, a photosensitive layer, a dye fixing layer and a white reflective layer are laminated on a transparent or opaque support. Preferred embodiments include, for example, transparent or opaque support/photosensitive layer/white reflective layer/dye fixing layer, transparent support/dye fixing layer/white reflective layer/photosensitive layer, and the like. Another typical form in which a photosensitive element and a dye fixing element are coated on the same support includes, for example, JP-A-56
−67840, Canadian Patent No. 674082, U.S. Patent No.
As described in No. 3730718, there is a form in which part or all of the photosensitive element is peeled off from the dye fixing element, and a peeling layer is coated at an appropriate position. The photosensitive element or dye fixing element may be in the form of an electrically conductive heating layer as a heating means for thermal development or diffusion transfer of the dye. In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta and cyan, the light-sensitive element used in the present invention comprises at least three layers of silver halide, each sensitive to a different spectral region. It is necessary to have an emulsion layer. Typical combinations of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions include a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, a green-sensitive emulsion layer,
A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and an infrared-sensitive emulsion layer, a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer. There are combinations of emulsion layers, etc. In addition, the infrared light-sensitive emulsion layer is 700 nm or more,
In particular, it refers to an emulsion layer that is sensitive to light of 740 nm or more. The light-sensitive material used in the present invention may have two or more emulsion layers sensitive to the same spectral region, depending on the sensitivity of the emulsion, if necessary. Each of the above emulsion layers and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer contains a dye-donating substance that releases or forms a yellow hydrophilic dye, and a dye-donating substance that releases or forms a magenta hydrophilic dye. It is necessary to contain at least one of a dye-donating substance and a dye-donating substance that releases or forms a cyan hydrophilic dye. In other words, each emulsion layer and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer must contain dye-donating substances that release or form hydrophilic dyes of different hues. If desired, add two dye-donating substances of the same hue.
You may use a mixture of more than one species. Particularly when the dye-providing substance is colored from the beginning, it is advantageous to contain the dye-providing substance in a layer separate from this emulsion layer. In addition to the above-mentioned layers, the photosensitive material used in the present invention may be provided with auxiliary layers such as a protective layer, an intermediate layer, an antistatic layer, an anti-curl layer, a release layer, and a matting agent layer, if necessary. In particular, the protective layer (PC) usually contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant, a UV absorber, and the like. Each of the protective layer and the intermediate layer may be composed of two or more layers. In addition, the intermediate layer contains a reducing agent to prevent color mixing.
UV absorbers and white pigments such as TiO ₂ may also be included. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing sensitivity. In order to impart each of the above-mentioned color sensitivities to a silver halide emulsion, each silver halide emulsion may be dye-sensitized using a known sensitizing dye to obtain the desired spectral sensitivity. The dye fixing element used in the present invention has at least one layer containing a mordant, and when the dye fixing layer is located on the surface, a protective layer can be further provided if necessary. Furthermore, a water absorption layer or a layer containing a dye transfer aid can be provided in order to sufficiently contain a dye transfer aid or to control the dye transfer aid if necessary. These layers may be adjacent to the dye fixing layer or may be applied via an intermediate layer. The dye fixing layer used in the present invention may be composed of two or more layers using mordants having different mordant powers, if necessary. In addition to the above-mentioned layers, the dye fixing element used in the present invention may be provided with auxiliary layers such as a release layer, a matting agent layer, and an anti-curl layer, if necessary. One or more of the above layers may include a base and/or base precursor to promote dye migration, a hydrophilic thermal solvent, an antifade agent to prevent color mixing of the dyes, a UV absorber, a dimensional stability agent, etc. A dispersed vinyl compound, a fluorescent whitening agent, etc. may be included to increase the brightness. The binder in the above layer is preferably hydrophilic, and transparent or translucent hydrophilic colloids are typical. For example, proteins such as gelatin, gelatin derivatives, polyvinyl alcohol, cellulose derivatives,
Natural substances such as polysaccharides such as starch and gum arabic, synthetic polymeric substances such as dextrin, pullulan, polyvinyl alcohol, polyvinylpyrrolidone, and water-soluble polyvinyl compounds such as acrylamide polymers are used. Among these, gelatin and polyvinyl alcohol are particularly effective. In addition to the above, the dye fixing element may have a reflective layer containing a white pigment such as titanium oxide, a neutralization layer, a neutralization timing layer, etc. depending on the purpose. These layers may be coated not only in the dye-fixing element but also in the photosensitive element. The configurations of the above-mentioned reflective layer, neutralization layer, and neutralization timing layer are described in, for example, US Pat.
It is described in Canadian Patent No. 2983606, Canadian Patent No. 3362819, Canadian Patent No. 3362821, Canadian Patent No. 3415644, and Canadian Patent No. 928559. Furthermore, it is advantageous for the dye fixing element of the present invention to contain a transfer aid as described below. The transfer aid may be included in the dye fixing layer, or may be included in a separate layer. In the present invention, the transparent or opaque heat generating element when electrical heating is employed as the developing means can be made using conventionally known techniques as a resistance heating element. As a resistance heating element, there are two methods: a method using a thin film of an inorganic material exhibiting semiconductivity, and a method using a thin film of an organic material in which conductive fine particles are dispersed in a binder.
Materials that can be used in the former method include silicon carbide, molybdenum silicide, lanthanum chromate,
Barium titanate ceramics, tin oxide, zinc oxide, etc. are used as PTC thermistors.
Transparent or opaque thin films can be made by known methods. In the latter method, conductive particles such as metal particles, carbon black, and graphite are dispersed in rubber, synthetic polymers, and gelatin to produce a resistor with desired temperature characteristics.
These resistors may be in direct contact with the photosensitive element or may be separated by a support, intermediate layer, or the like. The image receiving layer in the present invention includes a dye fixing layer used in heat-developable color light-sensitive materials, and can be arbitrarily selected from commonly used mordants, among which polymer mordants are particularly preferred. Here, the polymer mordant includes a polymer containing a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing these quaternary cation groups, and the like. Polymers containing vinyl monomer units having a tertiary amino group are described in Japanese Patent Application No. 169012/1982, Patent Application No. 166135/1982, etc., and polymers containing vinyl monomer units having a tertiary imidazole group are described in Specific examples include Japanese Patent Application No. 58-226497;
58-232071, U.S. Pat. No. 4,282,305;
It is described in No. 4115124, No. 3148061, etc. Preferred specific examples of polymers containing vinyl monomer units having quaternary imidazolium salts include British Patent Nos. 2056101, 2093041, and British Patent Nos.
1594961, U.S. Patent No. 4124386, U.S. Patent No. 4115124
No. 4273853, No. 4450224, Japanese Unexamined Patent Publication No. 1973-
It is described in No. 28225 etc. Other preferred specific examples of polymers containing vinyl monomer units having quaternary ammonium salts include U.S. Pat.
No. 3958995, Patent Application No. 58-166135, No. 58-169012
No. 58-232070, No. 58-232072 and No. 59
-Described in No. 91620, etc. As a light source for image exposure for recording an image on a heat-developable photosensitive material, radiation including visible light can be used. In general, light sources used for normal color printing, such as tungsten lamps, halogen lamps such as mercury lamps and iodine lamps,
Various light sources can be used, such as xenon lamps or laser light sources, CRT light sources, fluorescent tubes, and light emitting diodes (LEDs). The heating temperature in the heat development step is as described above, but within this range, it is preferably 140°C or higher, particularly
The temperature is preferably 150°C or higher. The heating temperature in the transfer process is
Transfer is possible at a temperature ranging from the temperature in the heat development step to room temperature, but it is particularly preferable to use a temperature up to about 10° C. lower than the temperature in the heat development step. As a heating means in the development and/or transfer process, a simple hot plate, iron, hot roller, heating element using carbon, titanium white, etc. can be used. A dye transfer aid (for example, water) is added between the photosensitive layer of a heat-developable photosensitive material and the dye fixing layer of a dye fixing material to promote image transfer. It is also possible to apply a dye transfer aid to one or both of the fixing layers and then superpose them. The heating means in the transfer process is heated by passing between hot plates or heating by contacting with the hot plates (for example, JP
62635), heating by rotating and contacting a heated drum or heated roller (for example, Japanese Patent Publication No. 10791/1979),
Heating by passing through hot air (for example, JP-A-53-
32737), heating by passing through an inert liquid kept at a constant temperature, heating by passing it along a heat source with a roller, belt, or guide member (for example, Japanese Patent Publication No. 44-2546), etc. I can do it. Alternatively, a layer of an electrically conductive material such as graphite, carbon black, or metal may be applied to the dye-fixing material in an overlapping manner, and an electric current may be passed through this electrically conductive layer to heat it directly. The heating temperature applied in the transfer step can be in the range from the temperature in the heat development step to room temperature, but is particularly preferably 60° C. or higher, and 10° C. or more lower than the temperature in the heat development step. Example 1 A method for making a silver iodobromide emulsion will be described. Dissolve 40g of gelatin and 26g of KBr in 3000ml of water. The solution is kept at 50°C and stirred. Next, a solution of 34 g of silver nitrate dissolved in 200 ml of water is added to the above solution over a period of 10 minutes. Then, a solution of 3.3 g of KI dissolved in 100 ml of water was added over 2 minutes. The pH of the silver iodobromide emulsion thus prepared is adjusted, and excess salt is removed by sedimentation. Thereafter, the pH was adjusted to 6.0 to obtain a silver iodobromide emulsion with a yield of 400 g. Next, a method for preparing a benzotriazole silver emulsion will be described. 28g gelatin and 13.2g benzotriazole in water
Dissolve in 3000ml. This solution is kept at 40°C and stirred. A solution of 17 g of silver nitrate dissolved in 100 ml of water is added to this solution over 2 minutes. Adjust the pH of this benzotriazole silver emulsion,
Allow to settle and remove excess salt. Then PH 6.0
A yield of 400 g of benzotriazole silver emulsion was obtained. Next, we will describe how to make a gelatin dispersion of a dye-providing substance (which has the same meaning as the above-mentioned image-forming substance; the same shall apply hereinafter). 5 g of yellow dye-donating substance (1), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate, 10 g of tri-iso-nonyl phosphate, 0.3 g of o-dodecyloxythiophenol as a surfactant. Weigh out, add 30 ml of ethyl acetate, and heat to dissolve at about 60°C to make a homogeneous solution.
After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, use a homogenizer for 10 minutes.
Disperses at 10000RPM. This dispersion is referred to as a dispersion of a yellow dye-providing substance. A dispersion of a magenta dye-providing substance was prepared in the same manner as described above, except that magenta dye-providing substance (2) was used. Similarly, a cyan dispersion containing the cyan dye-providing substance (3) was prepared. Dye-donating substance (1) (2) (3) Next, how to make a gelatin dispersion of the compound of the present invention will be described. 3 g of the compound (30) of the present invention was added to 100 g of a 1% gelatin aqueous solution and ground for 10 minutes in a mill with 100 g of glass beads having an average particle size of about 0.6 mm. Glass beads were overseparated to obtain a gelatin dispersion of the compound of the present invention. Color photosensitive materials having a multilayer structure as shown in the following table were prepared from these materials.

【table】

[Table] D-1 D-2 Next, in the photosensitive material A, the compound (30) of the present invention
Compounds (5) and (7) of the present invention were used instead, and photosensitive materials B and C were prepared using the same recipe, respectively.
For comparison, a photosensitive material D not containing the compound of the present invention was also prepared in the same manner. Next, a method for forming an image-receiving material having an image-receiving layer will be described. First, gelatin hardener H-1 0.75g, H-2
0.25 g and 160 ml of water and 100 g of 10% lime-treated gelatin were mixed uniformly. This mixed solution was uniformly applied onto a paper support laminated with polyethylene in which titanium oxide was dispersed to form a wet film of 60 μm, and then dried. Gelatin hardener H-1 CH ₂ = CHSO ₂ CH ₂ CONHCH ₂ CH ₂ NHCOC
H ₂・SO ₂ CH=CH _2Gelatin hardener H−2CH ₂ =CHSO ₂ CH ₂ CONHCH ₂・CH ₂ CH ₂ NH
COCH ₂ SO ₂ CH=CH ₂ Next, 15 g of a polymer having the following structure was dissolved in 200 ml of water and uniformly mixed with 100 g of 10% lime-treated gelatin. This mixed solution was uniformly applied onto the above-mentioned coating material to form a wet film of 85 μm. This sample was dried and used as a dye fixing material. polymer (Intrinsic viscosity 0.3473...1/20MNa ₂ HPO ₄ Measured at 30℃ in aqueous solution) A tungsten light bulb is used for the color photosensitive material with the above multilayer structure, and the concentration changes continuously B.
The film was exposed to light at 2000 lux for 10 seconds through a G and R three-color separation filter, and heated uniformly for 20 seconds on a heat block heated to 150°C or 153°C. After soaking the image-receiving material in water, the above-mentioned heated photosensitive materials A to D were stacked on top of each other so that their film surfaces were in contact with each other. After heating on a heat block at 80° C. for 6 seconds, the image-receiving material was peeled off from the light-sensitive material, and a negative magenta color image was obtained on the image-receiving material. The density of this negative image was measured using a Macbeth reflection densitometer (RD-519), and the following results were obtained.

[Table] From the above results, even if the development temperature is increased by 3° C. by using the compound of the present invention, both the maximum density and the minimum density increase little. On the other hand, in the Comparative Example without addition, the fog increases significantly. Therefore, it can be seen that the compound of the present invention has a high temperature compensation effect. Example 2 A method of preparing a silver halide emulsion for the fifth layer will be described. Add 1000 ml of an aqueous solution containing potassium iodide and potassium bromide to a well-stirred aqueous gelatin solution (20 g of gelatin and ammonia dissolved in 1000 c.c. of water and keep warm at 50°C) and a silver nitrate solution (in 1000 ml of water). (1 mole of silver nitrate dissolved in) at the same time
pAg was added while keeping it constant. In this way, a monodisperse silver iodobromide octahedral emulsion (5 mol % of iodine) with an average grain size of 0.5 μm was prepared. After washing with water and desalting, 5 mg of chloroauric acid (water temperature 4) and 2 mg of sodium thiosulfate were added to perform gold and sulfur sensitization at 60°C. The yield of emulsion was 1.0 kg. Next, I will talk about how to make the emulsion for the third layer. A well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water at 75°C)
600 ml of an aqueous solution containing sodium chloride and potassium bromide, a silver nitrate aqueous solution (0.59 mol of silver nitrate dissolved in 600 ml of water), and the following dye solution () were simultaneously heated for 40 minutes. and added in equal drop amounts. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) having a dye adsorbed thereon with an average grain size of 0.35 μm was prepared. After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were added to carry out chemical sensitization at 60°C. The yield of emulsion was 600g. Dye solution () 160mg methanol 400ml Next, we will explain how to make the emulsion for the first layer. A well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water at 75°C)
600 ml of an aqueous solution containing sodium chloride and potassium bromide and an aqueous silver nitrate solution (0.59 mol of silver nitrate dissolved in 600 ml of water) were simultaneously added in equal drop amounts over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 μm was prepared. After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were added to carry out chemical sensitization at 60°C. The yield of emulsion was 600g. A benzotriazole silver emulsion was prepared in the same manner as in Example 1.

[Table] Next, we will explain how to make the dye fixing material. Dissolve 12g of lime-treated gelatin in 200ml of water,
16 ml of a 0.5M zinc acetate aqueous solution was added to this and mixed uniformly. This mixed solution was uniformly applied to a wet film thickness of 85 μm on a 100 μm white film support made of polyethylene terephthalate containing titanium dioxide. Next, the following coating solution was prepared on top of this, and it was applied uniformly to a wet film thickness of 90 μm and dried to prepare a dye fixing material. <Dye fixing layer coating solution prescription F> Polyvinyl alcohol (degree of polymerization 2000) 10% aqueous solution
120g Urea 20g N-methylurea 20g

[Formula] 12% aqueous solution (intrinsic viscosity 0.1726...measured at 30°C in 1% NaCl aqueous solution) 80g Compound (30) of the present invention (described in Example 1)
60ml <Dye fixing layer coating solution formulation G> Polyvinyl alcohol (degree of polymerization 2000) 10% aqueous solution
120g Urea 20g N-methylurea 20g

[Formula] 12% aqueous solution 80g water 60ml B, where a tungsten light bulb is used in the above multilayered color photosensitive material and the temperature changes continuously.
It was exposed to light at 2000 lux for 1 second through a G and R three-color separation filter. Thereafter, it was heated uniformly for 30 seconds on a heat block heated to 140°C. This photosensitive material and the previously prepared dye-fixing material were placed on top of each other so that their film surfaces were in contact with each other, and the mixture was heated to 130°C.
Immediately after passing it through a heat roller, it was heated on a heat block at 120°C for 30 seconds. Immediately after heating, the dye-fixing material was peeled off from the light-sensitive material, and yellow, magenta, and cyan color images corresponding to the B, G, and R three-color separation filters were obtained on the dye-fixing material, respectively. The maximum and minimum densities of each color were measured using a Macbeth reflection densitometer (RD519).
The results are as follows.

[Table] As shown above, it can be seen that when the compound of the present invention is added to the dye fixing layer, it has the effect of suppressing the increase in fog during the transfer process. Example 3 Weigh out 10 g of the dye-donating substance (4), 0.5 g of sodium succinate 2-ethylhexyl ester sulfonate, and 10 g of tricresyl phosphate, add 20 ml of cyclohexanone, and dissolve by heating at 60°C to form a homogeneous mixture. It was made into a solution. 10 of this solution and lime-processed gelatin
After stirring and mixing with 100 g of % aqueous solution, the mixture was emulsified and dispersed using a homogenizer. Next, a photosensitive material H was prepared as follows. (a) 5.5 g of the silver iodobromide emulsion of Example 1 (b) 0.5 g of 10% gelatin aqueous solution (c) 2.5 g of the dispersion of the above dye-providing substance (d) 1 ml of 10% ethanol solution of guanidine trichloroacetic acid (d ) 2,6-dichloro-4-aminophenol
10% methanol solution 0.5ml (f) 5% aqueous solution of the compound with the following structure 1ml (g) Gelatin dispersion of the compound (30) of the present invention
0.5ml (h) water 6ml (4) The above (a) to (h) were mixed and heated to melt, and then coated on a polyethylene terephthalate film to a wet film thickness of 85 μm. A photosensitive material H was prepared by further coating gelatin at 1.5 g/m ² as a protective layer on this film. Using the above photosensitive material H using a tungsten light bulb,
Imagewise exposure for 10 seconds at 2000 lux, 140°C or
The mixture was heated uniformly for 30 seconds on a heat block heated to 143°C. Next, this was treated in the same manner as in Example 1, and the following results were obtained.

[Table] It can be seen from the above table that the effects of the compounds of the present invention are remarkable even in light-sensitive materials containing a dye-donating substance that releases a dye through a coupling reaction with the oxidation product of a developer. Example 4 5 g of dye-donating substance (5) having the following structure, 4 g of electron donor having the following structure, 0.5 g of sodium succinate 2-ethylhexyl ester sulfonate, 10 g of tricresyl phosphate, and cyclohexanone
20 ml was added and heated to about 60°C to dissolve. The rest was carried out in the same manner as in Example 3 to prepare a dispersion of the reducible dye-providing substance. Dye-donating substances (5) electron donor Example 3 Dye-donating substance (4) in photosensitive material H
Light-sensitive materials were prepared in exactly the same manner as described above except that the dispersion of the reducible dye-providing substance was used instead of the dispersion of the reducible dye-providing substance. This photosensitive material was exposed and processed in the same manner as in Example 3, and the measurements were as follows.

[Table] The above table confirms the effectiveness of the compound of the present application also in light-sensitive materials containing the above-mentioned reducible dye-providing substance capable of forming a positive image with respect to a silver image. Example 5 Preparation of gelatin dispersion of coupler 2-dodecylcarbamoyl-1-naphthol 5
g, 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate, and 2.5 g of tricresyl phosphate (TCP), and 30 ml of ethyl acetate.
was added and dissolved. 10% of this solution and gelatin
Stir and mix 100g of the solution, and use a homogenizer to
Dispersed for 10,000 RPM for minutes. Next, photosensitive material J was prepared as follows. (a) Silver iodobromide emulsion (from Example 1) 10 g (b) Gelatin dispersion of coupler 3.5 g (c) 0.25 g of guanidine trichloroacetic acid dissolved in 2.5 cc of ethanol (d) Gelatin (10% aqueous solution) ) 5g (e) 2,6-dichloro-p-aminophenol
(f) Gelatin dispersion of the compound (30) of the present invention (as described in Example 1) 0.2 g dissolved in 15 c.c. Apply to a wet film thickness of
It was dried to produce a photosensitive material. Using this photosensitive material with a tungsten light bulb, 2000
Imagewise exposure was made for 5 seconds at lux. Thereafter, when the film was heated uniformly for 20 seconds on a heat block heated to 150°C or 153°C, a negative cyan image was obtained. Measure this concentration using a Macbeth transmission densitometer (TD-504).
When the measurement was carried out using the following, the following results were obtained.

[Table] As shown above, it can be seen that the compounds of the present invention have an excellent temperature compensation effect. Example 6 Next, a black and white example will be described. Photosensitive material K was prepared as follows. (a) Silver iodobromide emulsion (as described in Example 1) 1 g (b) Silver benzotriazole emulsion (as described in Example 1) 10 g (c) 10% ethanol solution of guanidine trichloroacetic acid 1 c.c. (d ) 5% methanol solution of the compound shown by the following structural formula 2c.c. (e) Gelatin dispersion of compound (30) of the present invention (described in Example 1) 1c.c. The above coating solution was coated on a polyethylene terephthalate support to a wet film thickness of 60 μm and dried. Using this photosensitive material with a tungsten light bulb,
Imagewise exposure was made for 5 seconds at 2000 lux. then 130
30°C or on a heat block heated to 133°C.
After uniform heating for seconds, a negative brown image was obtained. This concentration was measured using a Macbeth transmission densitometer (TD-
504), the following results were obtained.

[Table] As shown above, it can be seen that the compounds of the present invention have an excellent temperature compensation effect.

Claims (1)

[Scope of Claims] 1. An image forming method comprising a heating step characterized by heating in the presence of a compound represented by the following general formula (). In the formula, X represents a carbon atom necessary to complete a benzene ring or a naphthalene ring, and R can be converted into a hydroxyl group or a dissociated product thereof in a heating step.
Represents a group represented by (A), (B) or (C) below. Q represents an aryl group or a substituted aryl group. Further, Q may be bonded to [Formula] TIME or PUG directly or via another atom. TIME represents a timing base. PUG stands for photographic useful group. n represents 0 or an integer. However, R ¹¹ and R ¹² may be the same or different, and each is a substituted or unsubstituted alkyl group, a cycloalkyl group, a substituted or unsubstituted alkenyl group, an aralkyl group, a substituted or unsubstituted aryl group. represents a group selected from a group, a heterocyclic residue, an alkylthio or aryloxy group, an alkylthio or arylthio group, and a substituted or unsubstituted amino group. Further, R ¹¹ and R ¹² may be combined with each other to form a 5- or 6-membered ring.