JPH0533780B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an image forming method having a heating step, and more particularly to a heat-developable image forming method containing a development inhibitor-releasing compound. (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 to 555, Published April 1978 Video information page 40, US Patent No. 3152904, No. 3301678, No. 3392020,
No. 3457075, British Patent No. 1131108, No. 1167777
issue and Research Disclosure Magazine, June 1978 issue, pages 9-15 (RD-17029). For information on how to obtain a color image,
Many methods have been proposed. Regarding the method of forming a color image by combining an oxidized developer and a coupler, U.S. Pat.
P-aminophenol-based reducing agents have been published in Belgian Patent No. 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. (Problems to be Solved by the Invention) However, since the supply of photographically useful reagents from a developer or the like cannot be expected, all necessary reagents must be incorporated in the photosensitive material in advance. Therefore, when a certain photographic reagent is generated at the start of development, or generated, released, or diffused at different timings, it is important to determine how selectively or in parallel the desired reactions can be performed. , is the biggest technical challenge. In particular, after the start of development, for the purpose of suppressing fog due to overdevelopment, stopping development after a certain period of time, and suppressing uneven image density due to uneven heating, etc.
The technology of producing, releasing, and diffusing a development inhibitor at a certain timing is an extremely important technology for determining the image quality of photothermographic materials. Such timing technology for releasing photographic reagents in conventional conventional or instant photography systems includes a polymer barrier layer that becomes permeable in a timely manner, and a protective group that deprotects the active site of the reagent during development. Although techniques for blocking the timing are known, they cannot be used in the thermal development system or cannot obtain sufficient effects, and the emergence of a new timing technique has been awaited. Therefore, an object of the present invention is to provide a timing technique for releasing a photographically useful reagent in an image forming method that includes a heating step.
The object of the present invention is to provide a compound that exhibits a development inhibiting effect after a certain period of time has elapsed. Another object of the present invention is to provide an image forming method that includes a heating step that provides a stable image with little fog and less chance of image unevenness. (Means for Solving the Problems) The objects of the present invention are achieved by an image forming method having a heating step characterized by heating in the presence of a compound represented by the following general formula (1) or (2). It was done. In the above general formulas (1) and (2), R ₁ and R ₂
are a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic residue, a carboxyl group or its salt, a halogen atom, a cyano group, an alkyl or arylsulfonyl group, and a sulfamoyl group, respectively. groups, carbamoyl groups, alkoxy or aryloxycarbonyl groups, di or mono alkyl or arylphosphoryl groups, di or mono alkyl or arylphosphinyl groups, alkyl or arylsulfinyl groups,
It represents an acyl group, an amino group, an acylamino group, an acyloxy group, or a group included in X described below. X represents a photographically useful group, preferably a development inhibitor group or a precursor group thereof that suppresses the redox reaction between the silver salt and the reducing agent. Note that R ₁ , R ₂ and X may further have another substituent in the group, or may be bonded to each other to form a ring. Ar represents an aryl group or a heterocyclic residue.
Ar may further have another substituent in the ring. Hereinafter, the specific configuration of the present invention will be explained in detail. In the above general formula (1) or (2), R ₁ and R ₂ are hydrogen atoms; halogen atoms; cyano groups; carboxyl groups or salts thereof; substituted or unsubstituted alkyl groups, cycloalkyl groups, alkenyl groups,
Alkynyl, aralkyl, aryl or heterocyclic residues; substituted or unsubstituted alkyl or arylsulfonyl groups; substituted or unsubstituted alkyl or arylcarbamoyl groups; substituted or unsubstituted alkoxy or aryloxycarbonyl groups; di- or Mono substituted or unsubstituted alkyl or arylphosphoryl groups; Di or mono substituted or unsubstituted alkyl or arylphosphinyl groups; Substituted or unsubstituted alkyl or arylsulfinyl groups; Substituted or unsubstituted acyl groups ; substituted or unsubstituted acylamino group; amino group to mono- or di-substituted or unsubstituted alkyl or arylamino group; substituted or unsubstituted acyloxy group; or a group included in X described below. In this case, preferable R ₁ has 1 to 1 carbon atoms.
8 substituted or unsubstituted alkyl groups, such as butyl group, hexyl group, octyl group; carbon number 6 to 12
substituted or unsubstituted aryl group, such as phenyl group, tolyl group, P-chlorophenyl group, P-
Methoxyphenyl group, etc.; substituted or unsubstituted aralkyl group having 7 to 14 carbon atoms, such as benzyl group,
β-phenethyl group, α-methylbenzyl group, etc.; alkenyl group having 2 to 8 carbon atoms, such as crotyl group,
Styryl group, etc.; Alkynyl group having 2 to 8 carbon atoms, such as ethynyl group, phenylethynyl group, etc.; cyano group; Substituted carbamoyl group, such as dimethylcarbamoyl group, diethylcarbamoyl group, morpholinocarbamoyl group, etc.; substituted or unsubstituted amino group, such as diethylamino group, piperidino group,
N-methylanilino group, etc.; carboxyl group: Furthermore, as groups included in X, substituted or unsubstituted alkylthio groups, arylthio groups, and heterocyclic thio groups are preferable. Among these, phenyl group, tolyl group, xylyl group, P-methoxyphenyl group, P-dimethylaminophenyl group and groups included in X are particularly preferred. On the other hand, R ₂ is a hydrogen atom; the number of carbon atoms described above is 1 to 8
a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group having 6 to 12 carbon atoms as described above; a cyano group; a halogen atom such as chlorine, bromine, iodine, etc.;
Substituted or unsubstituted alkyl or arylsulfonyl groups, such as methanesulfonyl, benzenesulfonyl, toluenesulfonyl, etc.; substituted sulfamoyl groups, such as dimethylsulfamoyl, diethylsulfamoyl, morpholinosulfonyl, etc.; Substituted carbamoyl group; the above-mentioned substituted amino group and further groups included in the above-mentioned X are suitable. Among these, particularly preferred are a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a P-chlorophenyl group, a P-methoxyphenyl group, and the like. Other substituents that can be bonded to R ₁ and R ₂ include halogen atoms, alkoxy groups, alkyl groups, hydroxyl groups, cyano groups, acyl groups, acylamino groups, acyloxy groups, nitro groups, dialkylamino groups, etc. There is. X represents a photographically useful group, preferably a development inhibitor group or its precursor group, and as the development inhibitor, the compound represented by the following general formula (3) is the most common and highly effective. However, Y is a compound containing at least one 5- or 6-membered heterocycle (preferably a sulfur atom,
Represents the atomic group necessary to form a ring containing a nitrogen atom or an oxygen atom. In general formula (3), the blocking group is bonded at a sulfur or nitrogen atom. Preferred examples of the development inhibitor represented by general formula (3) include the following compounds.

【formula】

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【formula】

[Formula] Here, R ₃ 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 have an appropriate substituent. Good too. In addition, as development inhibitor precursor substrates, there is a group of compounds that cause a thermal ring-closing reaction during thermal development to produce various heterocyclic compounds that function as development inhibitors. Examples of these include: In the formula, R ₄ and R ₅ represent a substituent selected from a hydrogen atom, an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, and a heterocyclic residue. Furthermore, compounds represented by R ₆ SH are also useful as development inhibitors. Here, R ₆ represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group, or aryl group having 6 to 22 carbon atoms. Among these, those with a particularly large suppressive effect have a carbon number of 10.
These are the above hydrophobic thiols. It is particularly preferable that these development inhibitors and their precursor substrates are bonded to the carbon atom of the parent body from the sulfur atom or nitrogen atom that is the active site. Ar represents a substituted or unsubstituted aryl group or a heterocyclic residue. Preferred examples of Ar include phenyl groups substituted with electron-donating groups, such as p-
Methoxyphenyl group, 2,4-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 4
-dimethylamino-2-methoxyphenyl group,
2,4,6-trimethylphenyl group, etc.; substituted or unsubstituted naphthyl group, such as 1-naphthyl group,
2-methoxy-1-naphthyl group, 4-methoxy-
1-naphthyl group, 2,4-dimethoxy-1-naphthyl group, etc.; 9-anthryl group; 9,10-antrylene group; 2-furyl group, 2-pyrrolyl group, 2-thienyl group, 3-indolyl group, etc. can be mentioned. The compound represented by the general formula (1) or (2) of the present invention is decomposed by the fragmentation reaction described below during thermal development, preferably to produce a development inhibitor substrate HX. The HX generated here diffuses to the surface of silver halide and other silver salt particles, where it forms a stable silver salt with silver ions, suppressing further development. However, as can be seen from the above-mentioned pathway, HX production requires a stepwise reaction, and here there is a time lag until the development inhibitor effect is expressed, that is, timing ability is expressed. Furthermore, in the case of a development inhibitor precursor substrate, a step of converting the precursor into a development inhibitor is also added, making it possible to provide even greater timing ability. As a result of the above, a technique has been established in which the effect of the development inhibitor is expressed after a certain period of time has elapsed after the start of development. The timing at which the development inhibitory effect is expressed can be adjusted by selecting R ₁ , R ₂ , X, and Ar. By selecting the optimal timing, it has become possible to prevent overdevelopment and eliminate fog without reducing image density and obtain stable images. Preferred specific examples of the compounds of the present invention are shown below, but the present invention is not limited thereto. Compounds of the invention can be synthesized in several ways. Examples include the reaction of oxime esters of β-halocinnamic acids with thiols, and the condensation of β-substituted mercaptocinnamic acids with oximes, but the most advantageous method is the reaction of propiolic acids with oxime esters, as shown in the scheme below. This method uses an addition reaction of thiols. A specific synthesis example is shown below. Synthesis of compound (2) 24g of phenylpropiolic acid and thionyl chloride
100ml of the mixture was heated to reflux for 2 hours. After cooling,
Excess thionyl chloride was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain phenylpropiolic acid chloride.
24.5g (bp.103-110°C/6mmHg) was obtained. 2-methoxy-1-naphthaldoxime 26.2g
and 300 ml of acetonitrile, 5.2 g of 60% oily sodium hydride was added under ice cooling. After stirring at 5°C for 30 minutes, the above acid chloride was added dropwise under ice cooling. After stirring for 1 hour at 5-10°C, the reaction solution was poured into cold water. After adding 600 ml of ethyl acetate to dissolve the crystals, the organic layer was separated, washed with water, and dried. The solvent was distilled off under reduced pressure, and 50 ml of ethyl acetate and 50 ml of n-hexane were added to the residue to collect crystals (yield: 31.4 g,
mp: 99−100℃). 16.5 g of the oxime ester obtained above, p-
Triethylamine 5% in a mixture of 14.7g dodecyloxythiophenol and 200ml acetonitrile
Added a drop. After the heat generation subsided, the mixture was heated at 50°C for 10 minutes. After cooling, the precipitated white crystals were collected and recrystallized from isopropanol-ethyl acetate-hexane to obtain 22.5 g of compound (2) (mp. 97-99°C). The compound represented by general formula (1) or (2) is usually added to the photosensitive layer of a photosensitive material, but is not particularly limited. Here, the photosensitive layer refers to a laminated colloid layer having at least one photosensitive silver salt emulsion layer on the support, which may also include an intermediate layer, a protective layer, etc., and a non-photosensitive layer on the opposite side of the support. This does not mean that there is a sexual back layer. Further, the amount of the compound represented by general formula (1) or (2) added is 0.1 to 20 mol%, preferably 0.5 to 5 mol%, based on the photosensitive silver salt. In the present invention, it is preferable to use silver halide as the photosensitive silver salt.
Produced according to the method described on pages 25 to 29 of the issue,
Silver halides containing the additives described therein and having the properties described therein can be used. 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. 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 type emulsions and nucleating agents can also be used. 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, it is desirable to use an organic metal salt relatively stable to light, particularly an organic silver salt, as an oxidizing agent together with the photosensitive silver halide. For details on organic silver salts that can be used, please refer to
No. 59-213978, pages 30-34. The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. These dyes and their details are described in Japanese Patent Application No. 59-213978, pages 34-38. The photosensitive material to which the present invention can be applied may contain a reducing agent. The reducing agent is preferably one known in the art or a dye image-forming compound having reducing properties. As specific examples of the reducing agent used in the present invention, those described on pages 61 to 64 of Japanese Patent Application No. 59-209563 can be used. The photosensitive material to which this method can be applied means any photosensitive material that forms a black-and-white image or a color image, and in particular, this method can be suitably used for heat-developable photosensitive materials. In the photosensitive material used in the present invention, when photosensitive silver halide is reduced to silver under high temperature conditions in order to obtain a color image, a mobile dye is generated in response to or inversely to this reaction. Alternatively, it may contain a releasing compound, ie a dye-donating 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 can be found, for example, in TH James, “The theory of the
"Photographic Process" 4th.Ed., pages 291-334 and 354-361, "Photographic Chemistry" 4th edition (Kyoritsu Shuppan) by Shinichi Kikuchi, pages 284-295, etc. A dye silver compound in which a salt and a dye are combined can also be cited as an example of a dye-donating substance.Specific examples of dye-donating substances 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. Another example of the dye-donating substance is a compound that has the function of releasing or diffusing a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula [LI]. (Dye-X) _o -Y [LI] Dye represents a dye group or a dye precursor group,
X represents a simple bond or linking group, and Y corresponds to or inversely corresponds to a photosensitive silver salt having a latent image (Dye-X) _o -Y, which causes a difference in the diffusivity of the compound represented by 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; n is 2
In this case, the two Dye-Xs may be the same or different. As a specific example of the dye-donating substance represented by the general formula [LI], for example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in U.S. Patent No. 3134764, U.S. Pat. ,
It is described in the same No. 3544545, the same No. 3482972, etc. Furthermore, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction is disclosed in JP-A-51-63618, and a substance that releases a diffusible dye through an intramolecular rewinding reaction of the isoxazolone ring is disclosed in JP-A-49. -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. Another method is to make the dye-releasing compound into an oxidized form without dye-releasing ability in advance, coexist with a reducing agent or its precursor, and after development, reduce it with the reducing agent that remains unoxidized to produce a diffusible dye. A method for releasing dye has also been devised, and a specific example of the dye-donating substance used therein is disclosed in Japanese Patent Application Laid-Open No. 110827-1983.
No. 54-130927, No. 56-164342, No. 53-
Described in No. 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 capable of producing 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, methods using these color developers pose a serious problem of image contamination due to oxidative decomposition products of the developer, so in order to improve this problem, we developed a method that does not require a developer and has its own reducing properties. Dye-donating compounds have also been devised. Representative examples can be found in the following documents. Definitions in the general formula are described in each literature. For example, US Patent No. 3928312, US Patent No. 4053312, US Patent No.
No. 4055428, No. 4336322, JP-A-59-65839,
No. 59-69839, No. 53-3819, No. 51-104343,
No. 51-104343, Research Disclosure No. 17465, U.S. Patent No. 3725062, U.S. Patent No. 3728113
Any of the various dye-donating substances described in Japanese Patent Application Laid-Open No. 116537/1983, etc. can be used in the present invention. Specific examples of the dye-donating substance used in the present invention include the compounds described on pages 60 to 91 of JP-A No. 59-84236, and among them, the compounds described in the above page range (1)～(3)、(10)～(13)、(1
6)
~(19), (28)~(30), (33), (35), (38)~(40), (42)~
(64) is preferred. Also, 82 of patent application No. 59-246468
Compounds described on page 83 are also useful. The dye-providing substance and photographic additive used in the present invention can be introduced into the layers of the photosensitive material by known methods such as the method described in US Pat. No. 2,322,027. In that case, the above-mentioned high-boiling point organic solvents, low-boiling point organic solvents, various surfactants, etc. can be used. The amount of the organic solvent used in the present invention is 10 g or less, preferably 5 g or less per 1 g of the dye-donating substance used. 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. A typical combination of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions is described in Japanese Patent Application No. 59-213973, pages 83-84, line 7. 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. The above-mentioned emulsion layers and/or non-photosensitive hydrophilic colloid layers adjacent to each emulsion layer are as described in Japanese Patent Application No. 59-213978, line 7 from the bottom of page 84 to line 8 of page 85. It is necessary to contain at least one kind. The photographic element of the color light-sensitive material used in the present invention is composed of a light-sensitive element that forms a dye image by forming or releasing a dye by heat development, and, if necessary, 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.
It is roughly divided into two types: one in which the coating is applied on two supports separately, and one in which the coating is applied on the same support. Also,
In the present invention, the compound of general formula (1) or (2) can be contained in the photosensitive element and/or the dye fixing element. The relationship between the photosensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer of the color photosensitive material used in the present invention is described in Japanese Patent Application No. 59-213978.
The relationships described on pages 81-82 are also applicable to the present application. In addition to the photosensitive silver salt emulsion layer, the photosensitive element may be provided with auxiliary layers such as a protective layer, an intermediate layer, an antistatic layer, an anticurl layer, a release layer, and a matting agent layer, if necessary. The coating method for each of these layers was published in a patent application filed in 1983.
The method described in No.-213978, pages 91-92 can be applied. 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. The dye fixing element 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. 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 contain bases and/or base precursors to promote dye migration, hydrophilic thermal solvents, antifade agents to prevent dye mixing, UV absorbers, and dimensional stability. A dispersed vinyl compound, a fluorescent whitening agent, etc. may be included to increase the brightness. The layer structure, binder, additive, mordant addition method, and installation position of the photosensitive element and/or dye fixing element are described in Japanese Patent Application No. 59-213978, pages 76-77, 86
The statements from page 10, line 10 to page 88, line 10 and the patent specifications described therein are also applicable to the present application. As a light source for image exposure to record an image on the photosensitive material used in the present invention, radiation including visible light can be used.
The light source described on page 92 of No. 213978 can be used. The photosensitive material used in the present invention may contain an image formation accelerator. 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 element layers. It has functions such as promoting the transfer of dyes from dye-fixing elements to dye-fixing elements, and from a physical science function, it has functions such as promoting the transfer of dyes from bases or base precursors, nucleophilic compounds, oils, hot solvents, surfactants, silver or silver ions, etc. It is classified as a compound with action. However, these physical groups generally have complex functions and usually have some of the above-mentioned promoting effects. For details of these, please refer to Japanese Patent Application No. 1983-213978 67
~Described on page 71. In the present invention, various development stoppers are used in combination with the compound of general formula (1) or () in order to always obtain a constant image despite fluctuations in processing temperature and processing time during thermal development of the photosensitive material. can be used. The term "development stopper" as used herein refers to a compound or its compound precursor that neutralizes the base or reacts with the base to reduce the base concentration in the film and stop development immediately after proper development, or a compound precursor thereof that interacts with silver and silver salts. A compound or a compound precursor thereof that inhibits development. Specific examples are described in the literature shown in Japanese Patent Application No. 59-213978, pages 72-73. Further, in the present invention, a compound that activates the development and stabilizes the image can be used in the photosensitive material. Specific compounds that are preferably used are described in the literature shown in Japanese Patent Application No. 59-213978, pages 73-74. In the present invention, the photosensitive material may contain an image toning agent if necessary. Specific examples of effective toning agents are described in Japanese Patent Application No. 59-213978, pages 74-75. In the present invention, the binders used in the photosensitive material may 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 substances include, in the form of latex,
In particular, there are dispersed vinyl compounds which increase the dimensional stability of photographic materials. In the present invention, the binder 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 support used for the light-sensitive element of the light-sensitive material and the optional dye-fixing element is one that can withstand the processing temperatures in the present method. As general supports, not only glass, paper, metal, and their analogs can be used, but also those listed as supports on pages 77 to 78 of the specification of Japanese Patent Application No. 59-213978 can be used. . The light-sensitive material used in the present invention may contain a dye transfer aid in order to promote the transfer of dye from the light-sensitive element to the dye-fixing element. 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 and an organic base is used. As these bases, those described in the section of the image formation accelerator can be 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 a manner in which the dye fixing element and/or the photosensitive element are wetted with the transfer aid. If the transfer aid is incorporated into the photosensitive element or dye fixing element, there is no need to supply the transfer aid from the outside.
As a method for applying a dye transfer aid to a photosensitive element layer or a dye fixing element layer, for example, Japanese Patent Application No. 1987-
There is a method described in No. 213978, page 93, line 6 from the bottom to page 94, line 2 from the bottom. In the present invention, a simple heating means such as a hot plate, an iron, a hot roller, etc. can be used as a means for developing a light-sensitive element of a light-sensitive material and/or transferring a mobile dye to a dye-fixing element. Particularly when electrical heating is employed, transparent or opaque heating elements can be fabricated using conventional techniques for resistive heating elements. As a resistance heating element, there are two methods: one uses a thin film of an inorganic material exhibiting a semiconductor, and the other uses a thin film of an organic material in which conductive fine particles are dispersed in a binder. Materials that can be used in these methods are
The materials described on page 89, lines 2 to 13 of Specification No. 213987 can be used according to the classification described therein, and according to the method and layer structure described therein. Regarding the mutual positional relationship of the heat generating element and the photosensitive element, the same as described in the fifth line from the bottom to the last line of page 89 can be applied. Further, it may be provided in a dye fixing element of a resistance heating element which is a heat generating element. In the present invention, when the process of thermally developing the photosensitive element of the photosensitive material and the process of transferring the dye to the dye fixing element are performed separately in time, the heating temperature of the photosensitive material in the heat developing process is approximately 80°C. C. to about 250.degree. C., but temperatures of about 110.degree. C. to about 180.degree. C. are particularly useful. The heating temperature for the photosensitive material in the transfer process can be transferred within the range from the temperature in the heat development process to room temperature, but in particular, the temperature at which the photosensitive material is heated is about 10°C higher than the temperature in the heat development process.
Temperatures as low as 0.degree. C. are more preferred. Furthermore, as detailed in Japanese Patent Application No. 59-218443, a method in which development and transfer are carried out simultaneously or consecutively is also useful. In this method, the above-mentioned image formation accelerator and/or dye transfer aid may be included in either or both of the dye fixing element and the photosensitive element in advance, or may be supplied from the outside. . In this method of performing development and transfer simultaneously or continuously, the heating temperature is 60℃ or higher,
That is, it is preferably below the boiling point of the solvent used for transfer. For example, if the transfer solvent is water, the
℃ or less is preferable. As for the pressure conditions and the method of applying pressure when the photosensitive element and the dye fixing element are brought into close contact with each other, the method described on page 96 of Japanese Patent Application No. 59-213978 can be applied. 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 dissolution is maintained 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-donating substance. Weigh out 5 g of the following yellow dye-donating substance (1), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate and 10 g of tri-iso-nonyl phosphate as surfactants, and add 30 g of ethyl acetate.
ml and heat to dissolve at about 60°C to make a homogeneous solution. This solution and a 10% solution of lime-processed gelatin
After stirring and mixing with 100g, use a homogenizer to
Disperse at 10,000 RPM for minutes. This dispersion is called a yellow dye-providing substance dispersion. 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 Next, how to make a gelatin dispersion of the compound of the present invention will be described. 3 g of exemplary compound (1) of the development inhibitor-releasing compound represented by the general formula (1) or (2) used in the present invention (hereinafter referred to as the compound of the present invention) was added to gelatin 1
% 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 compound (1) of the present invention. From these, color photosensitive elements A having a multilayer structure as shown in the following table were prepared.

【table】

[Table] Sensitizing dyes Next, in Photosensitive Element A, Compounds (2) and (5) of the present invention were used in place of Compound (1) of the present invention, and Photosensitive Elements B and C were prepared using the same recipe. Also, for comparison, photosensitive element D which does not contain the compound of the present invention
was made in the same way. Next, a method for forming a dye fixing element having a dye fixing 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 60 μm wet film, and then dried. Gelatin hardener H-1 CH ₂ =CHSO ₂ CH ₂ CONHCH ₂ CH ₂
NHCOCH ₂・SO ₂ CH=CH ₂ Gelatin hardener H-2 CH ₂ =CHSO ₂ CH ₂ CONHCH ₂・CH ₂ CH ₂
NHCOCH 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 element. polymer (Intrinsic viscosity (0.3473)...Measured at 30°C in a 1/20M Na ₂ HPO ₄ aqueous solution) A tungsten bulb was used for the color photosensitive element A with the above multilayer structure, and the concentration was continuously changed.
The film was exposed to light at 2000 lux for 10 seconds through a G and R three-color separation filter, and then heated uniformly for 20 or 30 seconds on a heat block heated to 150°C. After soaking the dye fixing element in water, the heated photosensitive elements A to D described above were stacked on each other so that their film surfaces were in contact with each other. After heating for 6 seconds on a heat block at 80°C, the dye-fixing element is peeled off from the photosensitive element.
Magenta and cyan images were obtained. The density of this negative image was measured using a Macbeth reflection densitometer (RD-519), and the following results were obtained.

【table】

【table】

Claims (1)

[Scope of Claims] 1. An image forming method comprising a heating step of heating in the presence of a compound represented by the following general formula (1) or (2). [In the above general formulas (1) and (2), R ₁ and
R ₂ is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic residue, a carboxyl group or a salt thereof, a halogen atom, a cyano group, an alkyl or arylsulfonyl group, respectively. , sulfamoyl group, carbamoyl group, alkoxy or aryloxycarbonyl group, di or mono alkyl or arylphosphoryl group, di or mono alkyl or arylphosphinyl group, alkyl or arylsulfinyl group, acyl group, amino group, It represents an acylamino group, an acyloxy group, or a group included in X described below. X represents a photographically useful group. Note that R ₁ , R ₂ and X may further have another substituent in the group, or may be bonded to each other to form a ring. Ar represents an aryl group or a heterocyclic residue.
Ar may further have separate substituents in the ring. ]