JPH0368372B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new method for forming dye images in a negative relationship to silver images by heating in substantially water-free conditions. The present invention further relates to a new light-sensitive material containing a reducing compound having a dye moiety which becomes immobile by reacting with a light-sensitive silver halide upon heating in a substantially water-free state. The present invention particularly relates to a new method for obtaining a dye image by moving imagewise distributed mobile dyes to a dye fixing layer by heating. Photography using silver halide has superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography.
It has traditionally been the most widely used. 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).
553-555 pages, 40 pages of development information published in April 1978,
Nebletts Handbook of Photography and
Reprography 7th Ed. (Van Nostrand 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). Many methods have been proposed for obtaining color images using a dry process. A method of forming a color image by combining an oxidized developer and a coupler is described in U.S. Pat. No. 3,531,286,
Phenylenediamine reducing agents and phenolic or active methylene couplers are used in U.S. Pat. , sulfonamide phenolic reducing agents are also disclosed in U.S. Patent No.
No. 4021240 proposes a combination of a sulfonamidophenolic reducing agent and a 4-equivalent coupler. However, in such a method, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, so that the color image becomes cloudy. To solve this problem, there are methods to remove the silver image by liquid processing or to transfer only the dye to another layer, such as a sheet with an image-receiving layer. It has the disadvantage that it is not easy to transfer. In addition, a method of introducing a nitrogen-containing heterocyclic group into a dye, forming a silver salt, and releasing the dye by heat development is described in Research Disclosure Magazine, May 1978 issue 54.
Described on page 58 RD-16966. With this method, it is difficult to suppress the release of dye in areas not exposed to light, and a clear image cannot be obtained, so it is not a common method. Further, regarding the method of forming positive color images by thermal 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. However, this method requires extra steps and materials, such as stacking and heating activator sheets to accelerate the bleaching of the dye, and the resulting color images may coexist during long-term storage. It had the disadvantage of being gradually reductively bleached by free silver and the like. Further, regarding the method of forming color images using leuco dyes, for example, US Pat. No. 3,985,565,
No. 4022617. However, this method has the drawback that it is difficult to stably incorporate the leuco dye into the photographic material, and the material gradually becomes colored during storage. Furthermore, the above-mentioned methods generally require a relatively long time for development, and the resulting images have the drawbacks of high blur and low density. The present invention provides a new method for forming positive dye images by heating in a substantially water-free state, and overcomes the drawbacks of hitherto known materials. An object of the present invention is to provide a new image forming method in which an immobile dye is generated when a silver image is formed by heating, and a negative image is formed on the silver image. The present invention provides a new silver halide color photosensitive material for heat development. The object of the present invention is to provide at least a photosensitive silver halide, a binder, a base or/and a binder on a support.
A light-sensitive material having a compound containing a dye moiety represented by the general formula This is achieved by a method of distributing Here, R ₁ , R ₂ , and R ₃ are each selected from among a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acylamino group, an alkylthio group, an arylthio group, and a halogen atom. Represents the selected group. Although X represents a divalent residue that connects the developer part and the dye part, the developer part and the dye part may be connected. Dye represents an image-forming pigment. G represents a hydroxyl group or a group that provides a hydroxyl group by the action of a nucleophile. The dye image of the present invention refers to multicolor and monochrome dye images, and the monochrome image in this case includes a monochrome image resulting from a mixture of two or more types of dyes. In the image forming method of the present invention, imagewise exposure is performed, and when heated in a state substantially free of water, a photosensitive silver halide having development nuclei is used as a catalyst to form a photosensitive silver halide and a dye portion represented by general formula A. An oxidation-reduction reaction occurs between the reducing compound having the
In a negative emulsion, a silver image and an oxidized product of the above-mentioned reducing compound are produced in the exposed area. General formula A
The reducing compound represented by becomes mobile when heated in the presence of a base, but its oxidized form is immobile, so in a negative emulsion, the dye is immobile in the exposed areas and mobile in the non-exposed areas. As a result, a dye image is formed which is an inverse function to the silver image, and by transferring this to a dye fixing material, a positive image can be obtained as a whole. The above relationship is completely reversed in the case of a positive emulsion, with a mobile dye forming in the exposed areas and an immobile dye forming in the non-exposed areas. The oxidation-reduction reaction between the silver halide and the reducing compound having a dye moiety (hereinafter simply referred to as a dye developer) of the present invention is characterized in that it occurs at high temperatures and in a dry state substantially free of water. Here, "high temperature" refers to a temperature condition of 80°C or higher, and "dry state, which does not substantially contain water" refers to a state in which the system is in equilibrium with the moisture in the air, but there is no water supply from outside the system. .
This situation is explained by “The theory of the
Photographic process"4th Ed. (Edited by T.
H.James, Macmillan) on page 374. The fact that a sufficient reaction rate is exhibited even in a dry state that does not substantially contain water can be confirmed from the fact that the reaction rate of a sample vacuum-dried for one day at 10 ^-3 mmHg did not decrease. Furthermore, the dye developer of the present invention can carry out a redox reaction with silver halide without the aid of a so-called auxiliary developer. This is an unexpected result based on previous knowledge of wet development at temperatures around room temperature. The above reaction proceeds particularly well in the presence of an organic silver salt oxidizing agent, resulting in high image density. Therefore, it is a particularly preferred embodiment to coexist an organic silver salt oxidizing agent. The compound represented by general formula (A) will be explained in detail below. Here, R ₁ , R ₂ , and R ₃ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acylamino group, an alkylthio group, an arylthio group, and a halogen atom. represents a group selected from
The alkyl and aryl groups in these groups further include alkoxy groups, hydroxyl groups, halogen atoms,
May be substituted with a cyano group, acyloxy group, alkoxycarbonyl group, acylamino group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, alkylsulfonylamio group, arylsulfonylamino group, ureido group, substituted ureido group . G represents a hydroxyl group or a group that provides a hydroxyl group by the action of a nucleophile. Although X represents a divalent residue that connects the reducing moiety and the dye moiety, the reducing moiety and the dye moiety may be directly coupled. In a preferred embodiment of the present invention, the substituent R ₁ ,
R ₂ and R ₃ are hydrogen atoms, alkyl groups having 4 or less carbon atoms,
A substituent selected from an alkoxy group having up to 4 carbon atoms and an alkylthio group having up to 4 carbon atoms, and G is a hydroxyl group or a trialkylsilyl ether of a hydroxyl group, a carboxylic acid ester, a carbonic acid ester, a sulfonic acid ester, a phosphoric acid ester It is a precursor of hydroxyl groups selected from esters. No linking group X or the divalent residues shown below are preferred. Alkylene, -O-, -S-,

[Formula], -SO ₂ -, -NHCO-, -alkylene-NHCO-,
Alkylene-NHSO ₂ −, Alkylene-SO ₂ NH
-, alkylene-CONH-, -NHCONH-,

[General formula]

In the above formula, A ₁ , A ₂ , A ₃ , and A ₄ may be the same or different, and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a substituted aryl group, and represents a substituent selected from heterocyclic residues, and
A ₁ and A ₂ or A ₃ and A ₄ may be linked to form a ring. Specific examples include H ₂ NSO ₂ NH ₂ , H ₂ NSO ₂ N
( _{CH3 ) 2 , H2NSO2N} ( _{C2H5 ) 2} , _{H2NSO2NHCH3 ,
H2NSO2N ( C2H4OH ) 2 , CH3NHSO2NHCH3 ,}

Examples include [Formula]. The above compounds can be used in a wide range of applications. A useful range is 20% by weight or less, more preferably 0.1 to 15% by weight of the dry coated film of the light-sensitive material. In the present invention, it is advantageous to use a water-releasing compound because it accelerates the dye-releasing reaction. A water-releasing compound is a compound that decomposes and releases water during thermal development. These compounds are particularly known for transfer printing of textiles, and were patented in Japan in 1970.
−NH ₄ Fe (SO ₄ ) ₂・12H ₂ O described in Publication No. 88386
etc. are useful. 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・Bisisothiuroniums such as trifluoroacetate),
Thiol compounds disclosed in West German Patent No. 2162714, 2-amino-2- described in U.S. Patent No. 4012260
Thiazolium compounds such as thiazolium trichloroacetate, 2-amino-5-bromoethyl-2-thiozolium trichloroacetate,
Bis(2-amino-
Compounds having α-sulfonylacetate as an acidic moiety such as 2-thiazolium)methylenebis(sulfonylacetate) and 2-amino-2-thiazolium phenylsulfonylacetate, as an acidic moiety described in U.S. Pat. No. 4,088,496. Compounds having 2-carboxycarboxamide are preferably used. In the present invention, a hot solvent can be contained. As used herein, a "thermal solvent" is a non-hydrolyzable organic material that is solid at ambient temperature but exhibits mixed melting points with other components at or below the heat treatment temperature used. Useful examples of the thermal solvent include compounds that can serve as solvents for developing agents, and compounds with high dielectric constants that are known to promote the physical phenomena of silver salts. Useful thermal solvents include polyglycols described in U.S. Pat. No. 3,347,675, such as polyethylene glycol with an average molecular weight of 1,500 to 20,000, derivatives of polyethylene oxide such as oleate ester, beeswax,
Monostearin, -SO ₂ -, high dielectric constant compounds having -CO- groups, such as acetamide, succinimide, ethyl carbamate, urea, methylsulfonamide, ethylene carbonate, polar substances described in U.S. Pat. No. 3,667,959, 4- Lactone of hydroxybutanoic acid, methylsulfinylmethane, tetrahydrothiophene-1,1-dioxide, 1,10-decanediol as described in Research Disclosure Magazine, December 1976 issue, pages 26-28,
Methyl anisate, biphenyl suberate, and the like are preferably used. In the case of the present invention, the dye-providing substance is colored, and although it is not so necessary to incorporate an anti-irradiation or anti-halation substance or dye into the light-sensitive material, in order to further improve the sharpness, 48-3692, U.S. Patent No. 3253921,
Filter dyes and absorbent substances described in specifications such as No. 2527583 and No. 2956879 can be contained. Preferably, these dyes are thermally decolorizable, such as those described in U.S. Pat. No. 3,769,019, U.S. Pat.
Dyes such as those described in No. 3,615,432 are preferred. The photosensitive material used in the present invention may contain various additives known as heat-developable photosensitive materials and layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, an AH layer, etc., as necessary. It can contain a chestnut layer and the like. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration, high contrast, sensitization), etc. Various surfactants may be included for various purposes. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic interfaces such as alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurine, sulfosuccinic acid Anions containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, etc. Surfactants; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridium Cationic surfactants such as heterocyclic quaternary ammonium salts such as , imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. Among the above-mentioned surfactants, it is preferable to include a polyethylene glycol type nonionic surfactant having an ethylene oxide repeating unit in the molecule in the photosensitive material. Particularly preferred are those having 5 or more repeating units of ethylene oxide. Nonionic surfactants that meet the above conditions are
It is widely used outside the field, and its structure, properties, and synthesis method are well known. Representative known documents include Surfactant Science Series
volume1.Nonionic Surfactants (Edited by
Martin J. Schick, Marcel Dekker Inc.1967),
Surface Active Ethylene Oxide Adducts
(Schoufeldt.N, Pergamon Press 1969), and the nonionic surfactants described in these documents that satisfy the above conditions are preferably used in the present invention. These nonionic surfactants can be used alone,
It can also be used as a mixture of two or more types. The polyethylene glycol type nonionic surfactant is used in an amount equal to or less than the weight of the hydrophilic binder, preferably 50% or less. The light-sensitive material of the present invention can contain a cationic compound having a pyridinium salt. An example of a cationic compound with a pyridinium group is
PSA Journal, Section B36 (1953),
USP2648604, USP3671247, Special Publication Showa 44-30074,
It is described in Special Publication No. 44-9503, etc. The photographic light-sensitive material and dye-fixing material of the present invention include:
The photographic emulsion layer and other binder layers may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) etc.), activated vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-
2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid,
Mucophenoxychloroic acid, etc.), etc. can be used alone or in combination. “Research Disclosure” for various additives
Additives such as plasticizers, sharpness improving additives, AH
These include dyes, sensitizing dyes, matting agents, optical brighteners, and anti-fading agents. In the present invention, as well as the heat-developable photosensitive layer, coating solutions for the protective layer, intermediate layer, undercoat layer, back layer, and other layers are prepared for each layer, and coated using the dipping method, air knife method, curtain coating method, or U.S. Patent No.
A light-sensitive material can be prepared by sequentially coating a support onto a support using various coating methods such as the hopper coating method described in No. 3,681,294 and drying the coating. Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095. Various exposure means can be used in the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, light sources used for normal color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, and
CRT light sources, fluorescent tubes, light emitting diodes, etc. can be used as light sources. The original drawing may be a line image such as a technical drawing, or a photographic image with gradation. It is also possible to photograph portraits of people and landscapes using a camera. The printing from the original drawing may be done by overlaying the original drawing by contact printing, reflection printing, or enlargement printing. In addition, images taken with video cameras and image information sent from television stations can be directly processed.
It is also possible to send the image to a CRT or FOT, form the image on a heat-developable material using a contact lens or a lens, and then print it. Furthermore, LEDs (light emitting diodes), which have recently seen great progress, are being used as exposure means or display means in various devices. this
It is difficult to create an LED that effectively emits blue light. In this case, to play a color image,
Three types of LEDs that emit green, red, and infrared light may be used, and the parts of the sensitive material that are sensitive to these lights may be designed to emit yellow, magenta, and cyan dyes, respectively. That is, the green-sensitive portion (layer) may contain a yellow dye-imparting substance, the red-sensitive area (layer) may contain a magenta dye-imparting substance, and the infrared-sensitive area (layer) may contain a cyan dye-imparting substance. Other combinations are also possible as required. In addition to the above method of directly attaching or projecting the original image, the original image illuminated by a light source can be
After reading the information using a light-receiving element such as a CCD and inputting it into the memory of a computer, etc., processing this information as necessary and performing so-called image processing, this image information is reproduced on a CRT and used as an image-like light source. There is also a method of directly emitting light from the three types of LEDs for exposure based on the processed information. In the present invention, after exposure of the photosensitive material, the resulting latent image is heated by heating the element at a moderately elevated temperature, e.g., from about 80°C to about 250°C for about 0.5 seconds to about 300 seconds. It can be developed by
As long as the temperature is within the above range, either high or low temperatures can be used by increasing or shortening the heating time. A temperature range of about 110°C to about 160°C is particularly useful. The heating means may be a simple hot plate, an iron, a hot roller, a heating element using carbon or titanium white, or the like. In the present invention, a specific method for forming a color image by heat development is to move a hydrophilic mobile dye. For this purpose, the light-sensitive material of the present invention has a light-sensitive layer () layer on a support, which contains at least silver halide, optionally an organic silver salt oxidizing agent and a dye-donating substance which is also a reducing agent thereof, and a binder. , a dye fixing layer ( ) that can receive a hydrophilic and diffusible dye formed by layers ( ). The above-mentioned photosensitive layer () and dye fixing layer () are:
They may be formed on the same support or on separate supports. The dye fixing layer ( ) and the photosensitive layer ( ) can also be peeled off. For example, after imagewise exposure, uniform heat development can be carried out, and then the dye fixing layer (2) or the photosensitive layer can be peeled off. In addition, when a photosensitive material with a photosensitive layer () coated on a support and a fixing material with a fixing layer () coated on a support are formed separately, the photosensitive material can be imagewise exposed to uniform light. After heating, the fixing material can be layered to transfer the mobile dye to the fixing layer (). There is also a method in which only the photosensitive material (2) is imagewise exposed, and then a dye fixing layer (2) is superimposed and uniformly heated. The dye fixing layer ( ) can contain, for example, a dye mordant for dye fixation. Various mordants can be used as the mordant, and polymer mordants are particularly useful. In addition to the mordant, a base, a base precursor, etc., and a hot solvent may be included. Especially the photosensitive layer () and the dye fixing layer ()
It is particularly useful to include a base, a base precursor, in the fixed layer () when the base and base precursor are formed on separate supports. The polymer mordants used in the present invention are polymers containing secondary and tertiary amino groups, polymers having nitrogen-containing heterocyclic moieties, polymers containing these quaternary cation groups, etc., and have a molecular weight of 5,000 to 20,000, particularly 10,000, 50,000. For example, US Patent No. 2548564, US Patent No. 2484430, US Patent No.
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in U.S. Patent Nos. 3148061 and 3756814;
Polymer mordants capable of crosslinking with gelatin etc. disclosed in US Pat. No. 3859096, US Pat.
No. 2798063, Japanese Unexamined Patent Publication No. 115228, No. 54-
Aqueous sol-type mordant disclosed in No. 145529, No. 54-126027, etc.; Water-insoluble mordant disclosed in U.S. Pat. No. 3,898,088; U.S. patent
A reactive mordant capable of forming a covalent bond with the dye disclosed in the specification of No. 4168976 (Japanese Unexamined Patent Publication No. 137333/1983);
No. 3642482, No. 3488706, No. 3557066, No.
No. 3271147, No. 3271148, JP-A-50-71332,
No. 53-30328, No. 52-155528, No. 53-125,
The mordant disclosed in the specification of 53-1024 can be mentioned. Other mordants described in US Pat. No. 2,675,316 and US Pat. No. 2,882,156 can also be mentioned. Among these mordants, for example, those that crosslink with the matrix such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) type mordants can be preferably used. Particularly preferred polymer mordants are shown below. (1) Groups that have a quaternary ammonium group and can be covalently bonded to gelatin (for example, aldehyde groups, chloroalkanoyl groups, chloroalkyl groups, vinylsulfonyl groups, pyridinium propionyl groups,
Polymers having vinylcarbonyl groups, alkylsulfonoxy groups, etc.) For example, (2) A reaction product of a copolymer consisting of a repeating unit of a monomer represented by the following general formula and a repeating unit of another ethylenically unsaturated polymer, and a crosslinking agent (eg, bisalkanesulfonate, bisarenesulfonate).

[Formula] R ^b ₁ : H, alkyl group R ^b ₂ : H, alkyl group, aryl group Q: divalent group R ^b ₃ , R ^b ₄ , R ^b ₅ : alkyl group, aryl group, or R ^b ₃ ~ At least two of R ^b ₅ may be combined to form a heterocycle. X: Anion (The above alkyl group and aryl group include substituted ones.) (3) Polymer represented by the following general formula x: about 0.25 to about 5 mol% y: about 0 to about 90 mol% z: about 10 to about 99 mol% A: Monomer having at least two ethylenically unsaturated bonds B: Copolymerizable ethylenically unsaturated Monomer Q: N, P R ^b ₁ , R ^b ₂ , R ^b ₃ : Alkyl group, cyclic hydrocarbon group, or at least two of R ^b ₁ to ^{R b} ₃ may be combined to form a ring . (These groups and rings may be substituted.) (4) Copolymer consisting of (a), (b) and (c)

[Formula] or

[Formula] 3
Water-insoluble polymer having more than R ^b ₁ , R ^b ₂ , R ^b ₃ : Each represents an alkyl group, and the total number of carbon atoms in R ^b ₁ to ^{R b} ₃ is 12 or more. (The alkyl group may be substituted.) X: Anion Various known gelatins can be used as the gelatin used for mordanting. For example, it is also possible to use gelatin manufactured by different methods such as lime-treated gelatin and acid-treated gelatin, or gelatin obtained by chemically modifying the obtained gelatin such as phthalation or sulfonylation. Moreover, if necessary, it can be used after being subjected to desalting treatment. The mixing ratio of the polymer mordant and gelatin of the present invention and the coating amount of the polymer mordant can be easily determined by those skilled in the art depending on the amount of dye to be mordanted, the type and composition of the polymer mordant, and the image forming process to be used. However, the mordant/gelatin ratio is 20/80 to 80/20 (weight ratio), and the amount of mordant applied is 0.5
Preferably it is used at ~8 g/ ^m2 . The dye fixing layer () may have a white reflective layer. For example, a layer of titanium dioxide dispersed in gelatin can be provided over a mordant layer on a transparent support. The titanium dioxide layer forms a white opaque layer, and by viewing the transferred color image from the transparent support side, a reflective color image can be obtained. A typical fixative material used in the present invention is obtained by mixing a polymer containing an ammonium salt with gelatin and coating it on a transparent support. A variety of dye transfer solvents can be used to transfer the imagewise distributed mobile dye developer to the dye fixation layer. An appropriate dye transfer solvent can be selected depending on the transfer method. In the method of supplying a transfer solvent from the outside when transferring a mobile dye developer, water and a basic aqueous solution containing potassium soda, potash, and an inorganic alkali metal salt are used as the transfer solvent. . Also used are low boiling point solvents such as methanol, N,N-dimethylformamide, acetone, and diisobutyl ketone, and mixed solutions of these low boiling point solvents and water or basic aqueous solutions. The dye transfer solvent may be used in a manner that wets the image-receiving layer with the solvent. When a mobile dye developer is transferred, in a system in which no transfer solvent is supplied from the outside, the transfer solvent is incorporated into the light-sensitive material or the dye fixing material. In this method, the above-mentioned solvent may be used in microcapsule form, or may be incorporated as a precursor that releases the solvent upon heating. More preferred is a method in which a hydrophilic thermal solvent that is solid at room temperature and dissolves when heated is incorporated into the light-sensitive material or dye-fixing material. These hydrophilic hot solvents only need to be able to substantially assist the movement of the mobile dye developer generated by heat development to the dye fixing layer, so if they can be included in the dye fixing layer, The hydrophilic material can be contained in a photosensitive material such as a photosensitive layer, or in both a dye fixing layer and a photosensitive layer, or in a photosensitive material or in an independent dye fixing sheet having a dye fixing layer. A separate layer containing a hot solvent can also be provided. From the viewpoint of increasing the transfer efficiency of the dye to the dye fixing layer, it is preferable that the hydrophilic thermal solvent is contained in the dye fixing layer and/or the layer adjacent thereto. The hydrophilic thermal solvent is usually dissolved in water and dispersed in the binder, but it can also be used dissolved in alcohols such as methanol, ethanol, etc. Examples of the hydrophilic heat solvent used in the present invention include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. 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. Then silver nitrate
A solution of 34 g 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, we will discuss how to make a benzotriazole silver emulsion. 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 discuss how to make a gelatin dispersion of a dye developer. 5g of magenta dye developer (1), succinic acid-2
-Sodium ethyl-hexyl ester sulfonate
0.5g, tricresyl phosphate (TCP)
Weigh out 5 g, add 30 ml of ethyl acetate, and heat and dissolve at about 60°C to make a homogeneous solution. This solution and 100 g of a 10% solution of lime-treated gelatin were stirred and mixed, and then dispersed using a homogenizer at 10,000 RPM for 10 minutes. This dispersion is called a dispersion of dye developer (1). Next, how to make photosensitive coatings A and B will be described. Photosensitive coating A (a) 25 g of the above silver iodobromide emulsion (b) 33 g of a dispersion of dye-providing substance (10) (c) 5 ml of a 5% aqueous solution of a compound having the following structure (d) 12 ml of 10% ethanol solution of guanidine trichloroacetic acid (e) 8 ml of water After mixing and dissolving at least 8 ml of (a) to (e), it was coated on a polyethylene terephthalate film to a wet film thickness of 30 μm and dried. Furthermore, the following composition was applied as a protective layer thereon. (a) 35 g of 10% gelatin aqueous solution (b) 5 ml of 10% guanidine trichloroacetic acid solution in ethanol (c) 4 ml of 1% aqueous solution of sodium succinate-2-ethyl-hexyl ester sulfonate (d) Mixed with 56 ml of water. A photosensitive coating A was prepared by coating with a wet film thickness of 25 μm and then drying. Photosensitive coating B consists of (a) 10 g of benzotriazole silver emulsion, (b) 20 g of silver iodobromide emulsion, (c) 33 g of a dispersion of dye-providing substance (10), and (d) a 5% aqueous solution of a compound having the following structure. 5ml (e) 12.5 ml of a 10% ethanol solution of guanidine trichloroacetic acid (f) 7.5 ml of water was mixed and dissolved, and then coated on a polyethylene terephthalate film to a wet film thickness of 30 μm, and then dried. The protective layer was applied in the same manner as Coating A. Next, we will discuss how to make the dye fixing material. 10 g of poly(methyl acrylate-co-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1)
10% lime-processed gelatin, 100% dissolved in 200ml water
It was evenly mixed with g. This mixed solution was uniformly applied to a wet film thickness of 90 μm on a paper support laminated with polyethylene in which titanium dioxide was dispersed.
After drying, this sample is used as a dye fixing material having a mordant layer. The above photosensitive coatings A and B were imagewise exposed for 10 seconds at 2000 lux using a tungsten bulb. Thereafter, it was heated for 30 seconds on a heat block heated to 130°C. Next, the dye-fixing material was soaked in water and placed on top of the above sample so that the film surface was in contact with the sample. After heating for 6 seconds on a heat block at 80°C, the dye-fixing material was peeled off from the photosensitive material, and the sample was placed on top of the fixing material. A positive magenta dye was obtained. The density of this positive image for green light was measured using a Macbeth reflection densitometer (RD-519).
The results measured using this are shown in the table below.

[Table] Example 2 Dye developer instead of dye developer (1) in Example 1
Using 5g each of (2), (4), and (7), the same operations and treatments as for photosensitive coating B in Example 1 were carried out, and photosensitive coatings (C), (D), and (E ) was created. Using these photosensitive coatings (C), (D), and (E), the same treatment as in Example 1 was carried out, and the results shown in the table below were obtained. However, the reflection density was measured using light that passed through a filter corresponding to each color.

[Table] From the results of Examples 1 and 2, it was found that the dye developing agent of the present invention gives clear positive images. Example 3 Instead of the dye fixing material used in Example 1, another dye fixing material was prepared and used by the method described below. 10 g of poly(methyl acrylate-co-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1)
100g 10% lime processed gelatin dissolved in 200ml water
mixed evenly. This mixed solution was uniformly applied onto a polyethylene terephthalate film to a wet film thickness of 90 μm. On top of the film formed in this way, the following
After mixing and dissolving (k) to (o), the mixture was coated uniformly to a wet film thickness of 60 μm and dried.
Hereinafter, this second layer will be referred to as a hydrophilic thermal solvent layer. (k) Urea (hydrophilic heat solvent) 4g (l) Water 10ml (m) Polyvinyl alcohol (saponification degree 98%)
10% by weight aqueous solution 12g (n) Compound with the following structure 100mg (o) 5% of sodium dodecylbenzenesulfonate
Aqueous solution 0.5 ml Photosensitive materials A and B of Example 1 were exposed imagewise for 10 seconds at 2000 lux using a tungsten bulb. Thereafter, it was heated uniformly for 20 seconds on a heat block heated to 140°C. Next, place the dye fixing material in close contact with the coated side facing each other, and then heat it for 120 minutes on a heat block.
Heated at ℃ for 30 seconds. When the dye fixing sheet is peeled off from the photosensitive material,
A positive magenta color image was obtained on the dye fixing sheet.

Claims (1)

[Claims] 1. At least photosensitive silver halide on a support,
A photosensitive material containing a binder, a base or/and a base precursor, and a compound containing a dye moiety represented by general formula A is heated in a substantially water-free state after or simultaneously with imagewise exposure to make it mobile. A method of distributing pigment in an image. Here, R ₁ , R ₂ , and R ₃ are each selected from among a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acylamino group, an alkylthio group, an arylthio group, and a halogen atom. Represents the selected group. Although X represents a divalent residue that connects the developer part and the dye part, the developer part and the dye part may be connected. Dye represents an image-forming pigment. G represents a hydroxyl group or a group that provides a hydroxyl group by the action of a nucleophile.