JPS61238056A - Formation of image - Google Patents

Abstract

PURPOSE:To form an image high in image density and low in fog in a short time by heating a heat developable photosensitive material contg. a dye donor capable of producing or releasing a diffusive dye when photosensitive silver halide is reduced to silver at high temp., after imagewise exposure or at the same time as the exposure, and transferring said dye to a dye fixing layer. CONSTITUTION:The heat-developable photosensitive material layer formed on a support contains the dye donor capable of reacting with silver in accordance with a produced silver image or with silver halide in accordance with the nonimage parts and producing or releasing the diffusive dye. This photosensitive material is imagewise exposed and after or at the same time as the exposure, it is heated in the presence of water and an alkali or alkali precursor, and the produced or released dye is rapidly transferred to the dye fixing layer, thus permitting an image high in dye density and low in fog to be formed rapidly.

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming dye images by heating. Prior art and its problems Heat-developable photosensitive materials are well known in this technical field, and for information on heat-developable photosensitive materials and their processes, see, for example, Fundamentals of Photographic Engineering (published by Corona Publishing, 1979), pp. 553-555, 1978, April 4, 1978. Monthly issue video information 40 pages, Neblett's I
Nebletts Handbook o
f Photography and Reprogra
pht) 7th Ed, Van Nostrand Reinhold Company (Van No5tr
and Re1nhold Compan7) 32~
33 pages, U.S. Patent No. 3,152,904, U.S. Patent No. 3,3
No. 01,678, No. 3.392.020, No. 3,
457,075, British Patent No. 1.131,108;
No. 1,167.777 and Research Disclosure Magazine, June 1978 issue, pages 9-15 (RD-170
29). Many methods have been proposed for obtaining color images. Regarding a method of forming a color image by combining an oxidized developer and a coupler, U.S. Pat. No. 781,270 describes the p-7 minofenol-based reducing agent as described in Belgian Patent No. 802.519 and Research Disclosure September 1975, 31.3.
On page 2, a sulfonamidophenolic reducing agent is proposed, and in US Pat. No. 4,021,240, a combination of a sulfonamidophenolic reducing agent and a 4-equivalent coupler is proposed. However, in this method, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, so that the two-color image becomes cloudy. To solve this problem, there is a method of removing the silver image by liquid processing or transferring only one dye to another layer, for example, a sheet having an image-receiving layer. It has the disadvantage that it is not easy to transfer. Furthermore, one or more of the methods generally require a relatively long time for development, and the resulting images have the disadvantage of high fog and low density. In order to improve these drawbacks, the present inventors have provided an image forming method using silver halide in which a movable dye is formed in one image and transferred to a dye fixing layer (Japanese Patent Application Laid-Open No. 58-1991). -149046, 59-154445,
No. 59-165054, No. 59-16054, U.S. Patent No. 4,503,137, No. 4,474,867
No. 4,483.914, No. 4,455,36
(described in issue 3). In this method, a light-sensitive material containing silver halide and a dye-donating substance that acts as a reducing agent for silver halide at high temperatures and is itself oxidized to release a mobile dye is exposed to light or simultaneously. A movable dye is formed in the form of an image by heating in a state substantially free of water. Such an image forming method requires a step of forming an image-like mobile dye by heating and a step of moving this dye to a dye fixed layer. If these steps can be performed simultaneously, the processing can be speeded up and simplified. It is considered necessary to attempt various studies from this perspective. (2) Purpose of the Invention An object of the present invention is to provide a quick and simple image forming method that provides an image with high dye density and little fog when forming a dye image by heating. ■Disclosure of the Invention These objects are achieved by the present invention described below. That is, the present invention provides at least a photosensitive silver halide on a support, a binder, and when the photosensitive silver halide is reduced to silver under high temperature conditions. A light-sensitive material containing a dye-donating substance that produces or releases a diffusible dye in response to or inversely to this reaction is heated in the presence of water and a base and/or base precursor after or simultaneously with imagewise exposure. This image forming method is characterized in that the generated or released diffusible dye is transferred to a dye fixing layer during heating for development. ■Specific structure of the invention Below, the specific structure of the present invention will be explained in detail. In the image forming method of the present invention, a light-sensitive material is heated in the presence of water and a base and/or a base precursor after or simultaneously with imagewise exposure, and the generated or released diffusible dye is heated for development. Transfer to the dye fixing layer at the same time. The dye fixing layer used in the present invention may be provided in a photosensitive material having a photosensitive layer, or may be provided in a material provided separately from the photosensitive material. The base and/or base precursor used in the present invention can be incorporated into the light-sensitive material and also into the dye-fixing material having the dye-fixing layer when the dye-fixing layer is provided separately from the light-sensitive material.
Moreover, it can also be used in a state dissolved in the water used in the present invention. The amount of water in the present invention is at least 0.1 times the weight of the entire coating film of the photosensitive material and dye fixing material, preferably 0.1 times the weight of the entire coating film to the maximum swelling volume of the entire coating film. Within the range of the weight of water, more preferably within the range of 0.1 times the weight of the entire coating film to the weight of water corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film. be. The state of the film during swelling is unstable, and depending on the conditions, local bleeding may occur.To avoid this, add water equivalent to the maximum swelling volume of the entire coated film of the photosensitive material and dye fixing material. It is preferable that the amount is less than that amount. However, the effect of the present invention is the same even when the amount of water is greater than the above-mentioned amount, only the above-mentioned disadvantages occur, and the effect is exhibited in the same way as when the amount of water is within the desired range. Here, "transferring the diffusible dye to the dye fixing layer during heating for development" means transferring the diffusible dye to the dye fixing layer using the effect of heating for development. A typical example is a method in which development and dye transfer are performed in one high temperature state. In the present invention, development by heating is used, and the water is present simply to move the dye distributed in an image. Therefore, the so-called developing solution is developed in a film unit and developed at around room temperature. Development can be performed at a pH much lower than the pH of 11 during development in the color diffusion transfer method. Increasing the pH significantly increases fog, which is even more inconvenient. Therefore, the pH of the film during heating for development and dye transfer is preferably 12 or less, more preferably 11 or less to a neutral pH. In the present invention, the binder forming the coating film may be any binder as long as it is non-transferable, and the coating film may contain photosensitive silver halide, a dye-donating substance, a mordant, and a high-boiling organic solvent; Even if there are objects, the relationship of the present invention holds true in the same way. The maximum swelling volume can be determined by immersing the photosensitive material or fixed material with the coating film to be measured in the water used, and once it has sufficiently swollen, measure the length of the cross section with a microscope, etc., and determine the film thickness.
It can be determined by multiplying by the area of the coating film of the photosensitive material or dye fixing material in question. The method for measuring the degree of swelling is described in Photographic Science Engineering, Vol. 16, p. 449 (published in 1972).
There is a description in . The degree of swelling of a gelatin film varies significantly depending on the degree of hardening, but the degree of hardening is usually adjusted so that the film thickness at maximum swelling is 2 to 6 times the dry film thickness. The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other wood-philic colloid layer.
Examples include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2゜3-dihydroxydioxane, etc.) ), active vinyl compound (1,3,5-1-lyacryloyl-hexahydro-5-)riazine, 1.3
-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-
5-) Riazine etc. 2. Mucohalogen acids (mucochloric acid, mucophenoxychloric acid), etc. can be used alone or in combination. The water mentioned above may be supplied to the dye-fixing material, to the photosensitive material, or to both the dye-fixing material and the photosensitive material. In the present invention, water may be supplied by any method, for example, it may be ejected as a jet from pores, it may be wetted with a web roller, or it may be supplied by squeezing a pot containing water. It's okay,
It is not limited to these methods or other methods; it may also be incorporated into the material as crystal water or microcapsules. The water used in the present invention is not limited to so-called "pure water", but includes water in the widely customary sense, and may also be an aqueous solution containing the following base and/or base precursor, or methanol. It may be a mixed solvent with a low boiling point solvent such as , DMF, acetone, or diisobutyl ketone. Furthermore, it may be an aqueous solution containing a dye release aid, an accelerator, or a wood-philic thermal solvent, which will be described later. The bases of the present invention include hydroxides of alkali metals, alkaline earth metals, or quaternary alkylammoniums, carbonate monoheavy acid salts, borates, secondary and tertiary phosphates, quinolates, metaboric acids. Inorganic bases such as salts; organic bases such as aliphatic amines, aromatic amines, heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, and their carbonates, heavy acid salts, boric acid salts, secondary and tertiary phosphates, and the like. Further, examples of the base precursor of the present invention include precursors of the aforementioned organic bases. The base precursor referred to herein is one that releases a basic component by thermal decomposition or electrolysis. For example, trichloroacetic acid, cyanoacetic acid, acetoacetic acid, α
-Salts of thermally decomposable pacifying acids such as sulfonylacetic acids and the above organic bases, 2- as described in U.S. Pat. No. 4.088.496.
Examples include salts with carboxycarboxamide.
Other British Patent No. 998.945, U.S. Patent No. 3,2
Base precursors described in No. 20.846, JP-A-50-22625, etc. can be used. Further, the following compounds can be mentioned as compounds that generate a base by electrolysis. For example, electrolysis of various fatty acid salts can be cited as a typical method using electrolytic oxidation. Through this reaction, carbonates of alkali metals and organic bases such as guanidines and amidines can be obtained extremely efficiently. In addition, methods using electrolytic reduction include the production of amines by reduction of nitro and nitroso compounds, the production of amines by reduction of nitriles; p-amine phenols and p-amines by reduction of nitro compounds, azo compounds, azoxy compounds, etc. - Generation of phenylenediamines and hydrazines, etc. P-7 minophenols, p-phenylenediamines,
In addition to using hydrazines as bases, they can also be used directly as color imaging materials. Of course, it is also possible to generate an alkaline component by electrolyzing water in the coexistence of various inorganic salts. Preferred specific examples are shown below, but the invention is not limited to these. Lithium hydroxide, sodium hydroxide, barium hydroxide,
Sodium carbonate, cesium carbonate, sodium hydrogen carbonate,
Potassium carbonate, potassium hydrogen carbonate, sodium quinolate, dibasic sodium phosphate, dibasic potassium phosphate, tertiary
Sodium phosphate, tribasic potassium phosphate, potassium pyrophosphate, sodium metaborate, borax, aqueous ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, (CH3)2 NH, (C2Hs )2 NH1c3H
7NH2, HOC2H4NH2, (HOC2H4)2
NH2 (IOC2H4) 3N, H2NC2H4NH2, H2NC4Ha NH2. CH3NHO2H4NHCH3. (CH3)2 NC3Ha N (CH3)2, guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, P-toluidine trichloroacetic acid, 2-picoline trichloroacetic acid, guanidine carbonate, piperidine charcoal. acid salts, morpholine carbonate, tetramethylammonium trichloroacetate, etc. Hydrochloric acid and/or base precursors can be used alone or in combination of two or more. The amount of base and/or base precursor used in the present invention can be used within a wide range. When used in the photosensitive layer and/or dye fixing layer, it is appropriate to use the coating film in an amount of 50% by weight or less, more preferably 0.01% to 40% by weight. Ranges are useful. Further, when used in the present invention by dissolving it in water, the concentration is preferably from 0.005 mole/l to 2 mole/l. Especially 0,05 mole/l to 1 mole/
A concentration of 1 is preferable, and the amount of these additions has no direct relation to pH, when combined with dye-fixing materials, etc. This is because bases and the like may migrate to other layers. In the present invention, heating is performed, but in this application, since the solvent of water is relatively large, the maximum temperature of the photosensitive material is the aqueous solution in the photosensitive material (various additives dissolved in the added water).
Determined by the boiling point of The minimum temperature is preferably 50°C or higher; the boiling point of water is 100°C under normal pressure;
When heated above ℃, water may evaporate and the water may disappear, so it is preferable to cover the surface of the photosensitive material with a water-impermeable material or to supply high-temperature, high-pressure water vapor.
In this case, since the boiling point of the aqueous solution also rises, the temperature of the photosensitive material also rises, which is advantageous. The heating means may be a simple hot plate, an iron, a hot roller, a heat generating plate using carbon, titanium white, etc., or the like. The dye image of the present invention includes multicolor and monochrome dyes and images, and the monochrome image in this case includes a monochrome image formed by a mixture of 2N1 or more dyes. In the dye image forming method of the present invention, the diffusible dye generated in the area corresponding to or inversely corresponding to the silver image is fixed at the same time as development by simply heating in the presence of a small amount of water after or simultaneously with the image exposure. Can be transferred to layers. The image forming method of the present invention will be explained using a dye-donating substance having a reducing substrate as an example. That is, in the method for forming a dye image of the present invention, when image exposure is carried out and heat development is performed in the presence of water, for example, in negative emulsion t, an oxidation-reduction reaction occurs between the exposed light-sensitive silver halide and the reducing dye-donating substance. occurs, producing a silver image in the exposed area, while one dye-donating substance becomes an oxidant, so that a hydrophilic diffusible dye is released and a silver image and a diffusible dye are obtained in the exposed area. At this time, the presence of a dye release aid accelerates the above reaction. Due to the presence of water, the generated diffusible dye immediately moves to the dye fixing layer, and in this way a dye image can be obtained in a short time. When an autopositive emulsion is used, the process is the same as when a negative emulsion is used, except that a silver image and a diffusive dye are obtained in the unexposed areas. When photosensitive silver halide is reduced to silver under high temperature conditions,
Useful image forming methods using dye-donating substances that produce or release diffusible dyes in response to or inversely to this reaction include JP-A-58-149046 and JP-A-59-154.
No. 445, No. 59-165054, No. 59-1805
No. 48, U.S. Patent No. 4,503,137, U.S. Patent No. 4,4
No. 74,867, No. 4, 483. No. 914 and No. 4,455,363, patent application 1980
Examples include those described in No.-33491. In the present invention, a specific method for forming a color image by heat development is to transfer a hydrophilic diffusible dye. For this purpose, the photosensitive material of the present invention has a photosensitive layer (on a support) containing at least /\ silver halide, optionally an organic silver salt oxidizing agent, optionally a reducing agent, a dye-donating substance, and a binder. (I) and a dye-fixing layer (n) capable of receiving a hydrophilic and diffusible dye formed by (I). The above-mentioned photosensitive layer CI) and dye fixing layer (n) may be formed on the same support, or may be formed on separate supports. Dye fixing layer (■) and photosensitive layer CI
) can also be peeled off. For example, after imagewise exposure, uniform heat development can be carried out, and then the dye-fixing layer (■) or the photosensitive layer can be peeled off. Furthermore, when a photosensitive material having a photosensitive layer (I) coated on a support and a fixing material having a fixing layer (n) coated on a support are formed separately,
The diffusible dye can be transferred to the fixing layer (n) by imagewise exposing the photosensitive material, overlapping the fixing material, and uniformly heating it in the presence of water. The dye fixing layer (n) can contain, for example, a dye mordant to fix one dye. 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 heat solvent may be included. In particular, when the photosensitive layer (I) and the dye fixing layer (■) are formed on different supports, the base, the base, etc. It is particularly useful to include precursors in the fixed layer (n). In the present invention, the photosensitive material may be used as necessary. There are two main types of photosensitive element and dye fixing element that are used together with a dye fixing element to fix the dye, and the photosensitive element and dye fixing element are formed on separate supports: one is a peelable type and the other is a peelable type. It is a type. In the former peel-off type, after image exposure, the coated surface of the photosensitive element 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 reflection type or a transmission type, the support for one dye-fixing element can be selected as an opaque support or a transparent support. In addition, a white reflective layer may be coated if necessary. In the latter type, which does not require peeling, a white reflective layer is interposed between the photosensitive layer in the photosensitive element and the dye fixing layer in the dye fixing element. This white reflective layer may be coated on either the photosensitive element or the dye-fixing element.The support of the dye-fixing element must be a transparent support. Hereinafter, when one dye-fixing element is on a support separate from the photosensitive dye, it may be referred to as a dye-fixing material. 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. Another typical form in which a photosensitive element and a dye-fixing element are coated on the same support includes, for example, Japanese Patent Application Laid-Open No. 56-6784.
0, Canadian Patent No. 674°082, U.S. Patent No. 3,7
As described in No. 30,718, 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. When the light-sensitive element and the dye-fixing element are on the same support, they will simply be referred to as light-sensitive materials in the following. 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 elements used in the present invention are made of silver halide, each sensitive to at least three different spectral regions. It is necessary to have an emulsion layer. at least three molecules sensitive to different spectral regions
Typical combinations of two light-sensitive silver halide emulsion layers 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 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, and a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer.
Note that the infrared light-sensitive emulsion layer herein refers to an emulsion layer that is sensitive to light of 700 nm or more, particularly 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 woody colloid layer adjacent to each emulsion layer contains a dye-donating substance that releases or forms a yellow woody 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-providing substance that forms and a dye-providing 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, two or more dye-providing substances of the same hue may be mixed and used.
It is advantageous to contain one dye-donor substance in a layer separate from the emulsion layer, especially when the dye-donor substance is initially colored. 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, etc. The protective layer and the intermediate layer may each be composed of two or more layers. The intermediate layer may also contain a reducing agent to prevent color mixing, a UV absorber, and a white pigment such as TiO2.The white pigment is added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing sensitivity. You may. 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 can 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 corrosion inhibitor to prevent color mixing of wood-philic heat-solvent dyes, a UV absorber, and a dimensional stability agent. A vinyl compound, a fluorescent whitening agent, etc. may be included in the dispersion to increase the dispersion. The binder in the above layer is preferably hydrophilic, and transparent or semitransparent woody colloids are typical. For example, proteins such as gelatin, gelatin derivatives, polyvinyl alcohol, and cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, dextrin, pullulan,
Synthetic polymeric substances such as polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyvinyl compounds such as acrylamide polymers, and the like 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 configuration of the above-mentioned reflective layer, neutralization layer, and neutralization timing layer is described, for example, in U.S. Pat. No. 2,983,606. , 3.36
No. 2,819, No. 3, No. 362, No. 821, No. 3, 4
No. 15,644, Canadian Patent No. 928.559, etc. 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. The silver halide that can be used in the light-sensitive material of the present invention may be silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide. The halogen composition within the zero particles may be uniform, or may have a multiple structure with different compositions on the surface and inside (Japanese Patent Laid-Open No. 57-154232).
No. 5g-108533, No. 59-48755,
No. 59-52237, U.S. Patent No. 4,433,048
and European Patent No. 100,984), and tabular grains each having a thickness of 0.5 gm or less, a diameter of at least 0.6 gm, and an average aspect ratio of 5 or more (
U.S. Patent No. 4,414,310, U.S. Patent No. 4,435,4
No. 99 and OLS No. 3,241,64
6AI, etc.) or monodispersed emulsions with a nearly uniform particle size distribution (JP-A-57-178235, JP-A No. 58-1008)
No. 46, No. 58-14829, International Publication No. 831023
38Ai, European Patent No. 64.412A3 and European Patent No. 83
, 377A1, etc.) may also be used in the present invention. Two or more types of silver halides with different crystal habit, halogen composition, particle size, grain size distribution, etc. may be used together.Two or more types of monodispersed emulsions with different grain sizes are mixed to create gradations. It can also be adjusted. The grain size of the silver halide used in the present invention preferably has an average grain size of 0.001 gm to loILm, more preferably 0.001 gm to 5 pm.
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
A back-mixing method in which particles are formed in an excess of silver ions, or a Chondrald double-jet method in which the pag is kept constant, can also be employed. Furthermore, in order to accelerate the growth of one grain, 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. 4,650,75
No. 7, etc.). Epitaxially bonded silver halide grains can also be used (JP-A-56-16124, U.S. Patent No. 4.094,
No. 684). When silver halide is used alone without an organic silver salt oxidizing agent in the present invention, silver chloroiodide, silver iodobromide, silver chloride iodide, silver iodobromide, silver iodobromide, and Preference is given to using silver bromide. Such a silver salt can be prepared by, for example, adding a silver nitrate solution to a potassium bromide solution to form silver bromide particles. Further addition of potassium iodide yields silver iodobromide having the above properties. In the step of forming silver halide grains used in the present invention, ammonia is used as a silver halide solvent, and Japanese Patent Publication No. 47-1
Organic thioether derivatives described in No. 1386 or sulfur-containing compounds described in JP-A-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. Furthermore, for the purpose of improving high illumination failure and low illumination failure, water-soluble idium salts such as iridium (m, iv) chloride and ammonium hexachloroiridate, or water-soluble dium 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 therefore the Tardel 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 nitrogen-containing heterocyclic compounds (Japanese Patent Application Laid-Open No. 126526/1983).
No. 5B-215644). The silver halide emulsion used in the present invention may be a surface latent image type in which a latent image is mainly formed on the grain surface, or an internal latent image type in which a latent image is formed inside the grains. Direct inversion emulsions combining emulsions and nucleating agents can also be used. Internal latent image emulsions suitable for this purpose are disclosed in U.S. Pat. No. 2,592,250, U.S. Pat.
It is described in No. 41 etc. Preferred nucleating agents for combination in the present invention are U.S. Pat. No. 3,227,552, U.S. Pat. It is described in 4,266.013, 4,276.364, 0L52,635,316, etc. Also, Japanese Patent Application No. 60-033462, No. 59-25374
No. 5, No. 59-233767, No. 59-234476
No. 59-270399, No. 59-114734, No. 59-51719, No. 59-48306, No. 5
No. 9-17097, No. 58-233846, No. 58-
The emulsions described in Nos. 56878 and 59-120039 are also preferably used as emulsions in the present invention. As a method for forming the silver halide grains used in the present invention, a known single jet method or double jet method can be used.・Double jet method can also be used. In addition, a combination of these methods may be used.In any of the above-mentioned silver halide emulsion forming methods, either the known single-stage addition method or multi-stage addition method may be used, and the addition rate may be a constant rate. , or a stepwise or continuous rate change (this could be, for example, a soluble silver salt and/or
Alternatively, there is a method of changing the addition flow rate of these solutions while keeping the concentration of the halide constant, or a method of changing the concentration of soluble silver salt and/or halide in the additive solution while keeping the addition flow rate constant. (or a combination thereof). Furthermore, the stirring method of the reaction solution may be any known stirring method. Also, the temperature of the reaction solution during silver halide grain formation, p
H may be set in any way. The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g/m'' in terms of silver. An organic metal salt can be used in combination as an oxidizing agent. In this case, the photosensitive silver halide and the organic metal salt must be in contact or at a close distance. Among such organic metal salts, Organic silver salt is
It is particularly preferably used. When an organic metal salt is used in combination in this way, when the heat-developable photosensitive material is heated to a temperature of ao'c or higher, preferably 100°C or higher, the organic metal oxidant also undergoes redox using the latent image of silver halide as a catalyst. Organic compounds that can be used to form the above organic silver salt oxidizing agent include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and Examples of 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, and furoic acid. , linoleic acid, linuric acid, adipic acid, sebacic acid, succinic acid, acetic acid, acetic acid, or camphoric acid. Typical examples include silver salts derived from these fatty acids. Halogen or hydroxyl substituted products of these fatty acids, or Silver salts derived from aliphatic carboxylic acids having thioether groups, etc. 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,
Typical examples include silver salts derived from terephthalic acid, salicylic acid, phenylacetic acid, pyromellitic acid, or 3-carboxymethyl-4-methyl-4-thiazoline-2,000-ion. As a silver salt of a compound having a mercapto or thiocarbonyl group, 3-mercapto-4-phenyl-1,2
, 4-triazole, 2-mercaptobenzimidazole, 2-mercapto-5-7minothiadiazole, 2-
Mercaptobenzthiazole, S-furkylthioglycolic acid (alkyl group has 12 to 22 carbon atoms), dithiocarboxylic acids such as dithioacetic acid, thioamides such as thiostearamide, 5-carboxy-1-methyl-2-phenyl-4 -thiopyridine, mercaptotriazine, 2
-mercaptobenzoxazole, mercaptooxadiazole or 3-amino-5-benzylthio-1,2
, 4-triazole U.S. Pat. No. 4,123,274
Examples include silver salts derived from mercapto compounds described in the above. As a silver salt of a compound having an imino group. Benzotriazole or its derivatives described in Japanese Patent Publication No. 44-30270 or No. 45-18418, such as benzotriazole, alkyl-substituted benzotriazoles such as methylbenzotriazole, halogen-substituted benzotriazoles such as 5-chlorobenzotriazole, butyl carboimide Carboimidobenzotriazoles such as benzotriazole, JP-A-5
Nitrobenzotriazoles described in US Pat. No. 8-118639, sulfobenzotriazole, carboxybenzotriazole or a salt thereof, or hydroxybenzotriazole described in JP-A-58-118638, 1. 2.4-) Representative examples include silver salts derived from lyazole, IH-tetrazole, carbazole, saccharin, imidazole, and derivatives thereof. Also, Research Disclosure Magazine No. 170, 1702
9 (June 1978), organic metal salts other than silver salts such as silver salts and copper stearate, patent application No. 58-2
Silver salts of carboxylic acids having alkyl groups, such as phenylpropiolic acid described in No. 21535, can also be used in the present invention. The above organic silver salts are 0 per mole of photosensitive silver halide.
．． 0.01 to 10 mol, preferably 0.0 to 1 mol, can be used in combination. The total coating amount of photosensitive silver halide and organic silver salt is suitably 50 mg to 10 g/m'. In the present invention, when photosensitive silver halide is reduced to silver under high temperature conditions, a dye-donating substance is contained that generates or releases a diffusible dye in response to or inversely to this reaction. The diffusible dye is preferably one that forms an image when the photosensitive material used in the present invention is heated after imagewise exposure or simultaneously with imagewise exposure. 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. This method using a coupler, in which an oxidized product of the developer produced by an oxidation-reduction reaction between a silver salt and a developer reacts with the coupler to form a dye, is described in numerous documents. Specific examples of developers and couplers are given by, for example, T.H.
The Theory of the Photographic Process
Photographic process) 4th edition (4th Ed), pages 291-334 and 354-361, Makoto Kikuchi, "Photographic Chemistry" 4th edition (Yame Publishing), pages 284-295, etc. . Further, a dye silver compound in which an organic silver salt and a dye are combined can also be cited as an example of the dye-donating substance. Specific examples of dye silver compounds are published in Research Fist Disclosure Magazine, 1978, 5.
Monthly issue. Pages 54 to 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. Pat. No. 4,235,957.
No., Research Disclosure Magazine, April 1976 issue, pages 30-32 (RD-14433). Also, U.S. Pat. No. 3,985,565. Leuco dyes described in 4,022,617 and the like 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 - Correspondingly, a difference is caused in the diffusivity of the compound represented by (Dye-X)n-Y, or D.y
e is released, and the released Dye and (Dye-X)n-Y
represents a group having properties that cause a difference in diffusivity between the group and n represents 1 or 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 (LI), for example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in US Pat. No. 3,134,764.
No. 3,362,819, No. 3,597,200. Same No. 3.544.545, Same No. 3. 482. It is described in No. 972, etc. In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction is disclosed in JP-A No. 51-63,618, etc.
A substance that releases a diffusible dye by an intramolecular rewinding reaction of an inoxacilone ring is described in JP-A-49-111, 628 and the like. In all of these methods, the diffusible dye is released or diffused in areas where no development has occurred, and the dye is not released or diffused in areas where development has occurred. Otherwise, it is very difficult to obtain an image with a high S/N ratio because diffusion occurs in parallel. Therefore, in order to improve this drawback, the dye-releasing compound is made into an oxidized form without dye-releasing ability in advance. A method has also been devised in which a diffusible dye is released by coexistence with a reducing agent or its precursor, and the reducing agent that remains unoxidized after development is used to release a diffusible dye. . It is described in JP-A Nos. 53-110,827, 54-130,927, 56-164,342, and 53-35,533. 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 the reaction between a coupler having a diffusible dye as a leaving group and an oxidized form of a developer is disclosed in British Patent No. 1. , No. 330,524, Japanese Patent Publication No. 48-39,165, and U.S. Patent No. 3,443,940, etc., diffusion is caused by the reaction between a coupler having a diffusion-resistant group as a leaving group and an oxidized form of a developer. Substances that produce sex pigments are described in U.S. Pat. No. 3,227,550 and elsewhere. In addition, in systems using these color developers, image contamination due to oxidative decomposition products of the developer becomes a serious problem.
In order to improve this problem, dye-releasing compounds that do not require a developer and have reducing properties themselves have also been devised. Representative examples of the above dye-donating substances are shown below. Definitions in the general formula are described in each literature. U.S. Patent No. 3,928,312, etc. U.S. Patent No. 4,053,312, etc. U.S. Patent No. 4,055,428, etc. U.S. Patent No. 4,336,322, etc. -69839 JP 53-3819 JP 51-104343 JP 51-104343 JP 51-104343 Research Disclosure Magazine 17465 U.S. Patent No. 3.725.062 U.S. Patent No. No. 3,728,113 U.S. Pat. No. 3,443,939 Any of the various dye-providing substances described above can be used in the present invention. The following four embodiments are most preferred as such dye-donating substances. (1) A dye that forms a diffusible dye by causing a coupling reaction with an oxidation product of a reducing agent generated upon reduction of silver halide. (2) A substance that releases a diffusible dye by causing a coupling reaction with an oxidation product of a reducing agent generated upon reduction of silver halide. (3) A reducing agent that reacts with silver halide and causes an oxidation-reduction reaction with the remaining reducing agent to release a diffusible dye. (4) Something that stops dye release by reacting with the oxidation product of the reducing agent produced by reducing silver halide. By using these four types, there are advantages such as being able to obtain clear color images in a short time. next,
The above 49 cases will be explained in detail. Those that correspond to the aspect of (1) are the following general formula % formula % general formula Cp-X-Ba1last (A) the above general formula (
In A', Cp represents a coupler that is free of one hydrogen at its active site, which forms a color image by combining with the oxidized form of the reducing agent. In this case, the couplers include, for example, magenta couplers such as 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc., and yellow couplers such as acylacetamide couplers (such as benzoylacetanilides, baloylacetanilides); as cyan couplers, naphthol couplers,
Examples include phenol couplers and the like. The reducing agent in this case is one known as a color developing agent in the field of conventional color photography, particularly preferably a p-phenylenediamine developer or a p-7
Examples include minophenol-based developers. A preferred general formula of Cp- is shown below. H(A4) In the above formula, R1-R4 are each a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an acylamino group, an alkoxyalkyl group , aryloxyalkyl group, alkoxycarbonyloxy group, alkoxycarbonylamino group, alkoxycarbonyl group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, amine group, alkylamino group, dialkylamino group, arylamino group, Cycloalkylamino group, i-halogen, cyano group, acyloxyalkyl group, nitro group, alkylsulfonyl group, arylsulfonyl group, hydroxyl group, carboxyl group, sulfo group, ureido group, substituted ureido group, sulfamoylamino group, substituted sulfonyl group famoylamino group,
represents a substituent selected from an alkylsulfonyloxy group, an arylsulfonyloxy group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclic residue, an imide group, and a quaternary ammonium group; These substituents further include hydroxyl group, carboxyl group, sulfo group, alkoxy group, cyano group, nitro group, alkyl group, aryl group, aryloxy group, acyloxy group, acyl group, sulfamoyl group, substituted sulfamoyl group, carbamoyl group, substituted Carbamoyl group, acylamino group, alkylsulfonylamino group,
Arylsulfonylamino group, sulfamoylamino group, substituted sulfamoylamino group, imide group. The total number of carbon atoms of the substituents R1 to R4, which may be substituted with a halogen atom and a quaternary ammonium group, is less than 12, and each substituent has 8 or less carbon atoms. In the above general formula (A), X is called a leaving group other than a hydrogen atom in a coupler, and represents a group that leaves when the coupler is bonded to an oxidized form of a reducing agent. That is, alkoxy group, aryloxy group, acyloxy group, alkoxycarbonyloxy group, carbamoyloxy group, N-substituted carbamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylsulfonylamino group, arylsulfonylamino group, perfluoroacyl Amino group, sulfamoylamino group,
Substituted sulfamoylamino group, alkylsulfonyl group,
It represents a substituent selected from an arylsulfonyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, an arylazo group, a heterocyclic residue, and an imide group, and these substituents further include an alkyl group, an alkenyl group, Cycloalkyl group, aralkyl group, aryl group, halogen atom,
Alkoxy group, aryloxy group, acyl group, acylami7 group, acyloxy group, alkylsulfonylamino group, arylsulfonylamino group, alkylsulfonyloxy group, arylsulfonyloxy group, alkoxycarbonyl group, substituted ureido group, alkoxycarbonyloxy group, It may be substituted with an alkoxycarbonylamino group, and the total number of carbon atoms in X is 8 or more. In the above general formula (A), Ba1last- represents a ballast group such as 2,4-di-1-aminophenoxy group, alkyl group having 6 or more carbon atoms (e.g. n-octyl group, n-lysosyl group, etc.). can be mentioned. Those corresponding to the embodiment (2) have the following general formula % Formula % General formula C-LD (B) Here, C is a bond with the oxidant produced by the reaction between the reducing agent and the organic silver salt oxidizing agent. D represents a dye moiety for image formation; L represents a linking group between C and D, and the C-L bond is cleaved by the reaction between the oxidized product of the reducing agent and C. The substrate C that can bind to the oxidant produced by the reaction between the reducing agent and the organic silver salt oxidizing agent is an active methylene, active methine, phenol, or naphthol residue, and preferable substrates are represented by the following general formulas (Bl) to ( B7). R1, R2, R3, and R4 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group,
Aryloxy group, aralkyl group, acyl group, acylamino group, alkoxyalkyl group, aryloxyalkyl group, N-substituted rubamoyl group, alkylamino group, arylamino group, halogen atom, acyloxy group, acyloxyalkyl group, cyano group represents a substituent selected from among, and these substituents further include a hydroxyl group, a cyano group, a nitro group, an N-substituted sulfamoyl group, a carbamoyl group, an N-substituted rubamoyl group, an acylamino group, an alkylsulfonylamino group, It may be substituted with an arylsulfonylamino group, an alkyl group, an aryl group, an alkoxy group, a 7-aryloxy group, an aralkyl group, or an acyl group. Substrate C must have the function of releasing a diffusible dye by combining with the oxidized form of the reducing agent, and must also have a ballast group to prevent the dye-donating substance itself from diffusing into the dye-receiving image-receiving layer. The ballast group must be an alkyl group. Hydrophobic groups such as alkoxyfurkyl groups and aryloxyalkyl groups are preferred, and these ballast groups preferably have a total carbon number of 6 or more, and the total carbon number of the substrate C is preferably 12 or more. The linking group connects the substrate C and the dye moiety through a covalent bond, and at the same time functions as a leaving group in the reaction between the oxidized product of the reducing agent and the substrate C. The linking group is preferably a divalent residue selected from the following general formula. D=υ~3 n=1~3 -NHCONH- -NHS O2N HCON H- Here, R, R'' represent a hydrogen atom, a methyl group, or an ethyl group, and the benzene ring further represents a hydroxyl group or a sulfamoyl group. , a methyl group. May be substituted with an ethyl group, an alkoxy group, a hydroxyalkyl group, a hydroxyalkoxy group, an alkoxyalkoxy group, or a halogen atom. Among these linking groups, preferable ones have a total carbon number of 12 or less and are resistant to diffusion. Dyes with a high degree of compatibility give good results. Dyes that can be used as image-forming dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes,
There are indigoid dyes, carbonium ion dyes, styryl dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, etc., and a representative example is European Patent Publication No. 79.058.
It is expressed by the general formula on pages 25 to 34 of this issue, and specific examples thereof are those described on pages 36 to 42 of this issue. Further, specific examples of the compound represented by CLD are described, for example, on pages 43 to 51 of European Patent Publication No. 79,056. A dye corresponding to the embodiment (3) has the following general formula: % Dye is a dye that becomes diffusible when released from a dye-donating substance, and preferably has a wood-philic group. Available dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes,
These include nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes. It should be noted that these dyes can also be used in a temporarily shortened form that can be restored in color during development. Specifically, the dyes described in European Patent Publication No. 76.492 can be used. X represents a simple bond or linking group, for example -NR
- (R represents a hydrogen atom, an alkyl group or a substituted alkyl group) group, -802- group, -CO- group, alkylene group, substituted alkylene group, phenylene group, substituted phenylene group, naphthylene group, substituted naphthylene group, -〇- group, -5
〇- group and groups formed by combining two or more of these groups are included. q is 1. Y releases Dye correspondingly or inversely to the photosensitive silver salt having a latent image, and the released dye and Dye-X-
A group having a property that causes a difference in diffusivity between Y and the compound represented by Y is used. In this case, valid Y is, for example. Examples include a group represented by formula (CI). In the formula, Ba1l represents a ballast group, β' represents an atomic group necessary to form a carbocycle, for example, a benzene ring, and a carbocycle or a heterocycle is further fused to this benzene ring to form a naphthalene ring, a quinoline ring, A 5,6,7.8-tetrahydronaphthalene ring, a chroman ring, etc. may be formed. G71 is an alkyl group (including substituted alkyl groups),
For a specific example of this type of Y, see Japanese Patent Application Laid-Open No. 53-355.
No. 33 and No. 53-110827. A further suitable Y is a group represented by (C2). "ox (C2) is a group that gives α' or α'. α' is a hydroxy group, a primary or secondary amine 7 group,
is an oxidizable nucleophilic group such as a hydroxyamino group or a sulfonamide group or its precursor, α'' is a dialkylamino group or any group defined for α', and G51 is a carbon atom of 1 to 3. an alkylene group having 1 to 4 carbon atoms, a represents 0 or l, and G52 is an alkylene group having 1 to 4 carbon atoms.
It is a substituted or unsubstituted alkyl group containing 0 carbon atoms, or a substituted or unsubstituted 7-aryl group containing 6 to 40 carbon atoms, and G53 is an electrophilic group such as -CO-1-C5-. G54 is an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom, etc., and in the case of a nitrogen atom, a hydrogen atom, a carbon atom 1 to
It may be substituted with an alkyl group containing 10 or a substituted alkyl group, an aromatic residue containing 6 to 20 carbon atoms. 55B G , G , and G57 are each a hydrogen atom, a halogen atom, a carbonyl group, a sulfamyl group, a sulfonamide group, an alkyloxy group containing 1 to 40 carbon atoms, or the same as G52, and G55 and G5B are both A 5- to 7-membered ring may be formed. Also, G58 may be , but it represents G52, G55, and G58. A specific example of this Y is given in JP-A-53-110
No. 827, U.S. Patent No. 4.356.249, U.S. Pat.
It is described in No. 358,525. Roughly examples of Y include those represented by formulas (G3) and (C4). However, (NuO 1 and (Nu ox) 2 may be the same or different, and represent an oxidized nucleophilic group. Nu and Nu82 may be the same or different, and may be 11, and represent a nucleophilic group or its precursor. represents, and Z is
R84 and R85 represent a divalent atomic group that is electronegative with respect to the substituted carbon atom, each of R, R and R83 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an acylamino group, or R81 and R
62 forms a fused ring with the rest of the molecule when in adjacent positions on the ring, or R and R83 form a fused ring with the rest of the molecule, and each of R and R85 may be the same or different. , represents hydrogen, a hydrocarbon group, or a substituted hydrocarbon group, and a ballast group Ba1l of sufficient size in at least one of the substituents R, R, R, R or R135 makes the above compound non-containing. It exists for mobility. Specific examples of this type of Y are described in JP-A-54-130927 and JP-A-56-164342. (C1), (C2), (G3) and (r!A)
A chthondonor has been described. The general formula of things that fall under the aspect (4) is: It is represented by the general formula (C) given in the above-mentioned embodiment (3), and the symbols in the general formula are used synonymously. However, since the effective Y is different from the aspect (3), it will be explained below. Examples of effective Y include those listed in formula (C5). In the formula, α', α'', G , G , G , G ,
G , G , G and a have the same meanings as in the above formula (C2). A specific example of this type of Y is described in JP-A-51-63618. Further suitable Y include formulas (C6) and (C7). In the above formula, Nu, Nu, Z, R, R, R,
R and R85 have the same meanings as in formula 8 (C3) and (C4) above. Specific examples of this type of Y are described in JP-A-53-69033 and JP-A-54-130927. A further suitable Y is a group represented by formula (C8). In the formula, Ba1l and β' are the same as those in formulas (C1) and (7) above, and C71 represents an alkyl group (including a 1!-substituted alkyl group). It is described in 1972-111628 and 52-4819. Specific examples of imaging materials for use in the present invention are described in the patent documents cited above. In addition, diffusible dyes are derived from azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, etc., and this dye part is temporarily Specific examples of the dye moiety released from the dye-donating compound include those described on pages 37 to 59 of JP-A-59-84236. Among them, the following are preferred. Yellow dye (Dye-1) (Dye-2) (Dye-3) (Dye-4) Magenta dye (Dye-5) (Dye-6) (Dye-7) Cyan dye ( Dye-8) 1l (Dye-9) (Dye-10) p (Dye-11) u In the present invention, the dye-donating substance is described in U.S. Patent No. 2,32
They can be introduced into the layers of the photosensitive material by known methods such as the method described in No. 2,027. In that case, high-boiling organic solvents and low-boiling organic solvents can be used. Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used. In addition, a variety of surfactants can be used when dispersing the dye-donating substance in the hydrophilic colloid, including 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 per 1 g of the dye-donating substance used.
It is as follows. In the present invention, it is desirable to include a reducing substance in the light-sensitive material. Examples of the reducing substance include those generally known as reducing agents, as well as the above-mentioned dye-donating substances having reducing properties. Also included are reducing agent precursors that do not themselves have reducing properties but exhibit 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, amine phenols, In addition to catechols, p-phenylenecyamines, 3-pyrazolidinones, droxytetronic acid, ascorbic acid, 4-amino-5-pyrazolones, etc., T.H.
The Theory of the Photographic Process, by James H.
f the photographic processes
s) 4th Edition (Ed.), pages 291-334 can also be used. Also, JP-A-58
Reducing agent precursors described in No. 138,736, No. 57-40.245, U.S. Pat. Examples of more preferable reducing agents include the following. 3-pyrazolidones and their precursors [e.g. 1
-Phenyl-3-pyrazolidone. 1-2-phenyl-4,4-dimethyl-3-pyrazolidone,
4-hydroxymethyl-4-methyl-1-phenyl-3
-pyrazolidone, l-m-tolyl-3-pyrazolidone,
1-p-) Zyl-3-pyrazolidone, 1-phenyl-4
-Methyl-3-pyrazolidone, l-7enyl-5-methyl-3-pyrazolidone, l-phenyl-4゜4-bis-
(Hydroxymethyl)-3-pyrazolidone, 1,4-di-methyl-3-pyrazolidone, 4-methyl-3-pyrazolidone, 4,4-dimethyl-3-pyrazolidone, 1-(
3-chlorophenyl)-4-methyl-3-pyrazolidone, 1-(4-chlorophenyl)-4-methyl-3-pyrazolidone, 1-(4-tolyl)-4-methyl-3-pyrazolidone, 1-(2- tolyl)-4-methyl-3-pyrazolidone, 1-(4-tolyl)-3-pyrazolidone, 1
-(3-tolyl)-3-pyrazolidone, 1-(3-tolyl)-4,4-dimethyl-3-pyrazolidone, 1-(2-tolyl)-4,4-dimethyl-3-pyrazolidone,
-trifluoroethyl)-4,4-dimethyl-3-pyrazolidone, 5-methyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, l-phenyl-4-methyl-4-stearoyloxymethyl-3- Pyrazolidone, 1-phenyl-4-methyl-4-lauroyloxymethyl-3-pyrazolidone. 1-phenyl-4,4-bis-(lauroyloxymethyl)-3-pyrazolidone, 1-phenyl-2-7cetyl-3-pyrazolidone, 1-phenyl-3-7cetoxypyrazolidone], hydroquinones and their Precursors [e.g. hydroquinone, toluhydroquinone, 2゜6-dimethylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, t-octylhydroquinone, 2゜5-dimethylhydroquinone

[-Octylhide
Rokinone, pentadecylhydroquinone, 5-pentade
Sodium sylhydroquinone-2-sulfonate, p-
Benzoyloxyphenol, 2-methyl-4-benzo
yloxyphenol, 2-t-butyl-4-(4-k)
lorobenzoyloxy)phenol] In the present invention, the compound disclosed in U.S. Pat. No. 3,039,869
Combinations of various reducing agents can also be used, such as
can. In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 01 to 20 mol, particularly preferably 0.1 to 10 mol
be. The binder used in the present invention can be used alone or in combination.
It can be contained in combination. The binder of the present invention includes hydrophilic binders and hydrophobic polymers.
- can be used. As a wood-philic binder, a transparent or semi-transparent hydrophilic resin is used.
Representative examples include gelatin and gelatin derivatives.
, proteins such as cellulose derivatives, starch, and
Natural substances such as polysaccharides such as beer gum and polyvinyl pin
Water-soluble polyvinyl such as lolidon and acrylamide polymers
Other synthetic polymerizations, including synthetic polymerization substances such as compounds
Compounds, in the form of latex, provide dimension stability, especially for photographic materials.
There are dispersed vinyl compounds that increase properties. In the present invention, the heat-developable photosensitive material and the dye-fixing material have images.
Formation promoters can be used. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent.
Promotion of reaction 1 Production of dyes from dye-donating substances or pigments
promotion of reactions such as decomposition or release of mobile dyes;
, promoting the movement of dye from the photosensitive material layer to the dye fixing layer, etc.
It has a function, and from the physicochemical function, it is a base or a base protein.
Recursors, nucleophilic compounds, oils, hot solvents. Surfactants, compounds that interact with silver or silver ions
etc. However, these substance groups are generally complex
function, and combines some of the above-mentioned promoting effects.
It is usual to have. Below, these image formation accelerators are classified by function and explained.
Specific examples of each are shown, but this classification is for convenience only.
In reality, one compound has multiple functions.
There are many things. -〇Mitate'' button 1 Examples of preferable bases include alkali as an inorganic base.
Metal or alkaline earth metal hydroxides, secondary or
triphosphate, borate, carbonate, quinolinate, metaphosate
Urate; Ammonium hydroxide: Quaternary alkyl ammonium
hydroxides of other metals, etc.
, aliphatic amines (trialkyl amines) are used as organic bases.
amines, hydroxylamines, aliphatic polyamines)
: Aromatic amines (N-alkyl substituted aromatic amines,
N-hydroxylalkyl-substituted aromatic amines and bicarbonate
(p-(dialkylamino)phenylcomethanes)
, heterocyclic amines, amidines, cyclic amidines, groups
Examples include anidines and cyclic guanidines, especially pKa
is preferably 8 or more. b Precursor base As a precursor, it decomposes by decarboxylation by heating.
intramolecular nucleophilic substitution reaction of salts of organic acids and bases, Rossen
Amines are decomposed by reactions such as rearrangement and Beckmann rearrangement.
Chemicals that undergo some kind of reaction when heated, such as compounds that release
those that release a base through electrolysis, and those that release a base through electrolysis
Preferably, the compound is used. of the former type
Preferred base precursors include trichloroacetic acid described in British Patent No. 998.949, etc.
α-sulfonyl salts described in U.S. Pat. No. 4,060,420
salts of acetic acid, propiolic acids described in Japanese Patent Application No. 58-55.700
salt. 2-Power Lupoki as described in U.S. Pat. No. 4,088,498
Silyl poxamide derivatives, in addition to organic bases as base components.
Combination with pyrolytic acids using alkali metals and alkaline earth metals
salt (patent application No. 58-69.597), utilizing Rossen rearrangement.
The hydroxa described in Japanese Patent Application No. 58-43,860
Mucarbamates, patent application to produce nitriles by heating
Aldoxime carbame described in No. 58-31.614
Examples include Others include British Patent No. 998,945, U.S. Patent No. 3,
220,846, JP-A-50-22.625, British Patent No. 2,079,480, etc.
-cers are also useful. Specific examples of base precursors that are particularly useful in the present invention are:
It is shown below. Guanidine trichloroacetate, methyl guar trichloroacetate
Nidine, potassium trichloroacetate, phenylsulfonyl
Guanidine acetate, p-chlorophenylsulfonylacetate
Anidine, p-methanesulfonylphenylsulfonyl vinegar
guanidine acid, potassium phenylpropiolate,
Cesium nylpropiolic acid, phenylpropiolic acid
Guanidine, p-chlorophenylpropiolic acid guanidine
guani, 2,4-dichlorophenylpropiolic acid
Diguani, p-phenylene-bis-propiolic acid
gin, phenylsulfonylacetate tetramethylammonium
Tetramethylammonium phenylpropiolate
. In addition, the following compounds generate bases by electrolysis:
can be mentioned. For example, using electrolytic oxidation
Electrolysis of various fatty acid salts is cited as a representative method.
I can do it. This reaction produces alkali metals and guanidine.
Extremely efficient method for carbonate of organic bases such as compounds and amidines.
You can get a lot of money. Also, a method using electrolytic reduction
amines by reduction of nitro and nitroso compounds.
production of nitrites, production of amines by reduction of nitriles;
By reduction of toro compounds, azo compounds, azoxy compounds, etc.
p-7 minophenols, p-phenylenediamines
, production of hydrazines, etc. p-aminophenols, p-phenylenediamines,
Hydrazines are not only used as bases, but also as bases.
It can also be used as a direct color imaging material. Ma
In addition, alkali formation was achieved by electrolysis of water in the coexistence of various inorganic salts.
Of course, it is also possible to generate a portion. Examples of preferred nucleophilic compounds are listed below. ■Water and water-releasing compounds (ammonium alum,
Iron alum, etc.) ■Amines (octylamine, dodecylamine, octa
Decylamine, dicyclohexylamine, aniline, p
-Toluidine, p-7 nisidine, 2,4-xylidine, etc.
) ■ Amidines (acetamidine, benzamidine, N-
Methylacetamidine, imidacilline, tetrahydropiline
rimidine, etc.) ■Guanidines (guanidine, methylguanidine, N,
N-dimethylguanidine, 2-aminoimidacillin, ?
-aminotetrahydropyrimidine, 2-aminobenzi
(midazole, etc.) ■Hydroxylamines (hydroxylamine, N-methane, etc.)
methylhydroxylamine, 0-methylhydroxylamine
) ■Hydrazines (methylhydrazine, N,N-dimethyl
hydrazine, phenylhydrazine, etc.) ■Hydrazides (acetohydrazide, benzhydrazide, etc.)
, isonicotinic acid hydrazide, p-toluenesulfony
ruhydrazine, etc.) ■Oximes (acetoxime, benzaldoxime, salt
lytylaldoxime, etc.) ■Hydroxamic acids (acetohydroxamic acid, benzyl aldoxime, etc.)
Doloxamic acid, P-)luenesulfohydroxamic acid, etc.) Sulfonamides (benzenesulfonamide, p-)
-chlorobenzenesulfonamide, dodecylbenzene
sulfamide, etc.) Sulfamides (sulfamide, N,N-dimethyl sulfonamide, etc.)
active methylene compounds (malononitrile, acetoacetate, etc.)
Nilide, l-phenyl-3-methyl-5-pyrazolone, etc.
) @Alcohols (dodecanol, glycerin, pentae
Lythritol, p-xylylene glycol, etc.) ■ Thiols (hexadecanethiol, dodecylbenze
salts or precursors of the above compounds may also be used.
can. In the present invention, the compounds described in JP-A-57-194,202 and JP-A-59-680,521 are particularly useful.
be. - Examples of oils with a preferable one-onion kernel are shown below. Phthalic acid alkyl ester (dibutyl phthalate, di
octyl phthalate, etc.), phosphate esters (diphenylphthalate, etc.),
phosphate, triphenyl phosphate, tricrephosphate
diyl phosphate, dioctyl butyl phosphate),
Citrate esters (e.g. acetyl tributyl citrate)
), benzoic acid ester (octyl benzoate), alkyl
Amides (e.g. diethyl laurylamide), fatty acid esters
esters (e.g. dibutoxyethyl succinate, dioxin)
tyl azelate), trimesic acid esters (e.g.
tributyl rimesate) etc. =C1 Engineering''Lll ■Ureas (urea, N-methylurea, N,N-dimethylurea
■Urethanes (N-phenyl urethane, N-diphenyl urethane, etc.) ■Amides (N-methylformanilide, acetamide, etc.)
, benzamide, N,N-dimethylbenzamide, etc.) ■Pyridines (2-hydroxypyridine, 4-hydroxypyridine, etc.)
cypyridine, 4-hydroxymethylpyridine, etc.) ■Sulfonamides (in addition to the above compounds, N.N-diethyl-p-)luenesulfonamide, N-ethyl-
(rubenzenesulfonamide, etc.) ■Sulfone, sulfoxy
(phenylmethylsulfone, diphenylsulfone,
diphenyl sulfoxide, etc.) ■Esters (dimethyl terephthalate, glycerin tri-
Benzoate, pentaerythritol tetrabenzoate
) ■Ketones (benzophenone, ditolyl ketone, ditolyl ketone, etc.)
) ■Ethers (hydroquinone dimethyl ether, β-
(naphthyl methyl ether, etc.) ■Pyridinium salts (compounds described in Japanese Patent Application No. 184,298/1982, etc.) ■Ammonium salts (triethylbenzylammonium
Chloride, trimethyldodecyl ammonium bromide, etc.
) ■Phosphonium salts (triphenylphosphonium promi
), tributylbenzylphosphonium chloride, etc.) ■Polyalkylene oxides (compounds described in Japanese Patent Application No. 57-168,186, etc.) ■Imides (phthalimide, succinimide, hydant)
(in, phthalazinone, etc.) ■Nitrogen-containing heterocycles (compounds described in Japanese Patent Application No. 58-51.657, etc.) ■Thiols (compounds described in Japanese Patent Application No. 57-222.247, etc.)
compounds, etc.) @thioureas (tetramethylthiourea, N'-dimethylethylenethiourea, etc.) ■Thioethers (di(β-hydroxyethyl) sulfate, etc.)
(Fido, β-hydroxyethylbenzyl sulfide, etc.) The image-forming accelerator is used to form an image in the light-sensitive material or in the light-sensitive material.
Any dye-fixing material that fixes the mobile dye generated in
It may be built into one or both, or it may be built into both.
The built-in calendar also includes an emulsion layer, an intermediate layer, a protective layer, a dye fixing layer,
and may be incorporated in any layer adjacent to them.
, a form having a photosensitive layer and a dye fixing layer on the same support
The same applies to Image formation accelerators can be used alone or in combination.
However, it is generally better to use several types together.
A significant promoting effect can be obtained. Especially when using bases or base precursors in combination with other promoters.
When this happens, a remarkable promoting effect is expressed. Imaging promoters can be used in a wide variety of ways. example
For example, a base or base precursor can be added to a photosensitive material (or
0.01 to 50
% by weight, nucleophilic compounds range from 0.1 to 20% by weight,
oil and hot solvent from 0.1 to 75% by weight, and surfactant from 0.1 to 75% by weight.
Up to 50% by weight of binder, silver or silver ions
The number of compounds that interact with silver is 104 to 1 per mole of silver.
Interacts with silver or silver ions, preferably in the molar range
In the case of compounds with
Because both effects may be present, it is important to
It is more desirable to adjust the amount added as appropriate. In the present invention, fluctuations in processing temperature and processing time during thermal development are
However, in order to always obtain a constant image, various development stoppers are used.
can be used in photosensitive materials and dye fixing materials. The development stopper referred to here means that the base is removed immediately after proper development.
Neutralize or react with a base to lower the base concentration in the film and facilitate development.
Interacts with terminating compounds or silver or silver salts.
It is a compound that suppresses images. Specifically, by heating, acid
An acid precursor that releases
Electrophilic compounds, mercapto compounds or
Examples include nitrogen-containing heterocyclic compounds. 1 for acid precursors, for example, Japanese Patent Application No. 58-216.9
Oxime S described in No. 28 and No. 59-48,305
Rossen as described in Japanese Patent Application No. 59-85.834
By dislocation. Examples include compounds that release acids, which can be converted into bases by heating.
For electrophilic compounds that undergo substitution reactions, for example, Japanese Patent Application No. 59-85
．． Examples include the compounds described in No. 836. When the above development stoppers are used together with a base precursor
is preferred, in which case the base precursor/acid precursor
The value of the ratio (molar ratio) of 1/20 to 20/l is preferable.
more preferably 115 to 5/1. - Use of various antifoggants in the present invention
I can do it. As an antifoggant. Nitrogen-containing carboxylic acid described in Japanese Patent Application No. 58-43862
and phosphoric acids, or patent application No. 57-222247
The mercapto compound and its metal salt described in the issue are used.
Ru. These antifoggants have a concentration of 0.00 per mole of silver.
It is used in a concentration range of 1-10 molar. The silver halide emulsion used in the present invention is a methine dye.
The color used may be spectrally sensitized by other
The raw materials include cyanine pigment, merocyanine pigment, and complex cyanine pigment.
pigment, complex merocyanine pigment, holopolar cyanine
Pigments, hemicyanine pigments, styryl pigments and hemioxy
Includes sonol dyes. Particularly useful dyes are shea
Nin pigments, merocyanine pigments, and complex merocyanines
It is a pigment that belongs to pigments. These pigments contain cyanine as a basic heterocyclic nucleus.
Any nucleus commonly used for pigments can be applied.
i.e. viroline nucleus, oxazoline nucleus, thiazoline nucleus
, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selena
Zole nucleus, imidazole nucleus, tetrazole nucleus, pyridine
Nuclei, etc.; Nuclei in which alicyclic hydrocarbon rings are fused to these nuclei;
and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e.
, indolenine nucleus, benzindolenine nucleus, indole
nucleus, benzoxadol nucleus, naphthoxazole nucleus, base
Nzothiazole nucleus, naphthothiazole nucleus, benzoselenium
Suitable examples include sol nucleus, benzimidazole nucleus, and quinoline nucleus.
Can be used. These nuclei are substituted on carbon atoms
Good too. Merocyanine dyes are also ketogenic for complex merocyanine dyes.
Pyrazolin-5-one as a nucleus with methylene structure
nucleus, thiohydantoin nucleus, 2-thioxazolidine-2
, 4-dione nucleus, thiazolidine-2,4-dione nucleus,
- 5- to 6-membered heteromorphs such as danin nucleus and thiobarbic acid nucleus
A ring nucleus can be applied. Useful sensitizing dyes include, for example, German Patent No. 929.080, US Pat. No. 2,231,658, US Pat. No. 519,001, No. 2,912,329. Same No. 3,656,959. Same No. 3,672,897. Same No. 3,694,217. No. 4,025,349, No. 4,046,572. British Patent No. 1,242,588. Examples include those described in Japanese Patent Publication No. 44-14030 and Japanese Patent Publication No. 52-24844. useful sensitization
Specific examples of dyes include the following compounds. Specific examples of useful sensitizing dyes include the following compounds:
be. These sensitizing dyes may be used alone, but a combination of them may be used.
Combinations of sensitizing dyes may be used, especially those with superchromic sensitizing dyes.
Often used for emotional purposes. A typical example is U.S. Patent No. 2.888.545. 2,977.229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3.628 No. 964. Same No. 3,666.480, Same No. 3,872,898. Same No. 3.679.428. 3,703,377, 3,769,301, 3,814,609, 3,837,862. British Patent No. 4,026,707, British Patent No. 1,344,281, British Patent No. 1,507,803, and Japanese Patent Publication No. 43-4936. It is described in JP-A-53-12,375, JP-A-52-110,618, and JP-A-52-109,925. Along with the sensitizing dye, it itself spectroscopy
Substantially absorbs non-sensitizing dyes or visible light
If the emulsion contains a substance that exhibits supersensitization but does not
For example, a nitrogen-containing heterocyclic group may be substituted.
Minostyl compounds (e.g., U.S. Pat. No. 2,933,39
No. 0, as described in No. 3,635,721). Aromatic organic acid formaldehyde condensates (e.g.
3,743,510), cadmium salts
, an azaindene compound, and the like. The combinations described in U.S. Pat. Nos. 3,615,613, 3,615,641, 3,617,295, and 3,635,721 are particularly useful. These sensitizing dyes are contained in silver halide photographic emulsions.
They can be directly dispersed in the emulsion to
or water, methanol, ethanol, acetone,
For single or mixed solvents such as methyl cellosolve
They may be dissolved and added to the emulsion, or they may be added to the
Dissolved in a substantially water-immiscible solvent such as diethanol
After that, it is dispersed in water or parent wood colloid, and this dispersion is made into an emulsion.
In addition, those sensitizing dyes may be added as dyes.
Mix with lipophilic compounds such as donor compounds and add at the same time.
You can also It also dissolves those sensitizing dyes
In some cases, sensitizing dyes used in combination may be dissolved separately.
Also, the mixture may be dissolved. Also, emulsions
You can also add it at the same time as a mixture.
However, it can be added separately or at the same time as other additives.
It may be added to the emulsion and during chemical ripening.
Or it may be before or after that, or U.S. Patent No. 4,183.
No. 758, halogen according to No. 4,225,666
It may be carried out before or after nucleation of silver oxide grains. Also, Japanese Patent Application No. 59-257255, No. 59-25374
No. 4, No. 59-264079, No. 59-186855
No. 59-179035, No. 59-52774,
The sensitizing dye and addition method described in No. 5B-55701 are also included in the present invention.
It is preferably used as The amount added is generally less than 10-6 per mole of silver halide.
It is about 10-f mole. Hydrophobic compounds such as dye-donating substances used in the present invention are
1. Can be introduced into photosensitive materials by various known dispersion methods, and
body dispersion method, alkaline dispersion method, preferably latex dispersion method
A typical example is the oil droplet dispersion method, more preferably the oil droplet dispersion method.
can be mentioned. In the oil-in-water dispersion method, the boiling point is 1
High boiling point organic solvents above 75°C and low boiling point so-called supplements
Dissolved in either co-solvent alone or in a mixture of both.
Then water or gelatin aqueous solution in the presence of surfactant
finely dispersed in aqueous media. Examples of high boiling point organic solvents
is described in US Pat. No. 2.322.027. Dispersion may involve transfer and, if necessary, auxiliary solubilization.
By distilling the medium, washing noodles with water, or ultrafiltration, etc.
It may be used for coating after removal or reduction. Specific examples of high boiling point organic solvents include phthalate esters
(dibutyl phthalate, dicyclohexyl phthalate,
Di-2-ethylhexyl phthalate, didodecylphthalate
esters of phosphoric or phosphonic acids (such as
Riphenyl phosphate, tricresyl phosphate. 2-Ethylhexyl diphenyl phosphate, trisic
lohexyl phosphate, tri-2-ethylhexyl phosphate
sphate, tridecyl phosphate, tributoxye
chill phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexylbenzoate
, dodecyl benzoate, 2-ethylhexyl-p-h
droxybenzoate, etc.). Amide (diethyldodecanamide, N-tetradecylpi
lolidone), alcohols or phenols (e.g. lolidone), alcohols or phenols (e.g.
Stearyl alcohol, 2,4-di-tert-amino
phenol, etc.), aliphatic carboxylic acid esters (dimethylphenol, etc.), aliphatic carboxylic acid esters
Octyl azelate, glycerol tributyrate, i
Stearyl lactate, trioctyl citrate, etc.
), aniline derivative (N,N-dibutyl-2-butoxy
-5-tert-octylaniline, etc.), hydrocarbons
(paraffin, dodecylbenzene, diisopropyliluna)
Examples include phthalene, and as co-solvents, boiling point
Organic solvents with a temperature of about 30°C to about 160°C can be used.
, typical examples include ethyl acetate, butyl acetate, propio
ethyl phosphate, methyl ethyl ketone, cyclohexanone,
2-ethoxyethyl acetate, dimethylformamide
Examples include. Latex dispersion process, effects and latex for impregnation
A specific example of this is U.S. Pat. No. 4,199,363. OLS No. 2,541,274, and OLS
No. 2,541,230, etc. Photographic additives that are sparingly soluble in water should be dissolved in an appropriate high-boiling organic solvent.
oak, woody organic colloids, especially in solutions of gelatin
with the presence of a surfactant (usually an anionic surfactant)
dispersed in a wood-philic organic colloid layer (for example, a photosensitive emulsion)
layer, filter layer, back layer, anti-halesh recognition layer,
(intermediate layer, protective layer, etc.). Regarding the emulsification and dispersion method of such oil-soluble photographic additives,
For example, the following are known. Namely, U.S. Pat. No. 2,739,888, U.S. Pat. No. 3,352,681, and U.S. Pat. No. 2,360,290. Same No. 2,728,659, Same No. 3.700.453. It is described in JP-A-51-129.229 and the like. According to one embodiment of the invention, the boiling point is about 175°C or higher.
High-boiling organic solvents (e.g. dibutyl phthalate), or
is a low boiling point organic solvent (with a boiling point of about 30°C to about 150°C).
(for example, ethyl acetate) or a mixed solvent of both.
After dissolving the additive (e.g. coupler), add the surfactant.
mixed with a woody colloid (e.g. gelatin) solution containing
, then a high-speed rotary mixer, or colloid mill, etc.
It is emulsified and dispersed using an emulsifying machine, and this is then mixed with wood-loving colloids.
Added to photographic coating solution. Alternatively, the emulsification
The dispersion can be vacuum degassed to remove low-boiling organic solvents, or milk
After cooling the dispersion, cut it into small pieces and wash with water etc. to reduce the boiling point.
After removing the organic solvent, it is mixed with a hydrophilic colloid-containing solution.
may be added to photographic coating solutions prepared in this way.
By applying the prepared photographic coating liquid onto the support.
The photosensitive material of the present invention can be produced. The support used for the material in the present invention is
It is something that can be endured. Common supports include glass, paper, metal and
As well as analogues are used. Acetyl cellulose film, cellulose ester film
lum, polyvinyl acetal film, polystyrene film
film, polycarbonate film, polyethylene tele
Phthalate films and related films or
contains resin materials. U.S. Patent No. 3.634.089, U.S. Patent No. 3.725.0
No. 70, Patent Application No. 59-278812, same number 23580
The polyester described in No. 5 is preferably used. In the present invention, a photographic emulsion layer or other hydrophilic layer of a light-sensitive material is used.
The colloid layer contains coating aids, antistatic properties, improved slipperiness,
Emulsification dispersion, anti-adhesion and improvement of photographic properties (e.g. development
various surfactants for various purposes such as enhancement, contrast enhancement, sensitization)
It may also contain an agent. For example, saponins (steroids), alkylene oxa
derivatives (e.g. polyethylene glycol, polyethylene
lene glycol/polypropylene glycol condensate,
Liethylene glycol alkyl ethers or polyethylene
Tylene glycol alkyl aryl ethers, polyester
Styrene glycol esters, polyethylene glycol
Sorbitan esters, polyalkylene glycol alcohols
Kylamines or amides, silicone polyethylene
oxide adducts), glycidol derivatives (e.g.
Alkenylsuccinic acid polyglyceride, alkylphenol
polyglycerides), fatty acid esters of polyhydric alcohols
nonionic surfactants such as sugar alkyl esters, etc.
Agent; alkyl carboxylate, furkylsulfonate,
Alkylbenzene sulfonate, alkylnaphthalene
Sulfonates, alkyl sulfates, alkyl
acid esters, N-acyl-N-furkyltaurines
, sulfosuccinic acid esters, sulfoalkyl polyoxy
Cyethylene alkylphenyl ethers, polyoxyesters
Carbohydrates such as tyrene alkyl phosphates, etc.
Oxy group, sulfo group, phospho group, sulfate ester group, phosphoric acid ester group
Anionic surfactants containing acidic groups such as stellate groups; amino
Acids, aminoalkyl sulfonic acids, aminoalkyl sulfur
Acids or phosphoric esters, alkyl betaines, amines
Amphoteric surfactants such as oxides; alkylamine salts
, aliphatic or aromatic quaternary ammonium salts,
Heterocyclic quaternary ammonium such as Nizilam and Imidazolium
salts, and phosphoniol containing aliphatic or heterocyclic rings.
cationic surfactants, such as surfactants or sulfonium salts.
Can be used. Among the above surfactants, Japanese Patent Application No. 57-188186
repeating unit of ethylene oxide in the molecule described in
Polyethylene glycol type nonionic surfactant with
It is preferable, particularly preferable, to include it in the photosensitive material.
In particular, the number of repeating units of ethylene oxide is 5 or more.
It is desirable that the The photosensitive material of the present invention includes a cation having a pyridinium salt.
It can contain a chemical compound. Examples of cationic compounds having a pyridinium group include PSA Journal, 5section B.
3B (1953). U.S. Patent No. 2,648,604. U.S. Patent No. 3,671,247. Special Publication No. 44-30074. It is described in Japanese Patent Publication No. 44-9503, Japanese Unexamined Patent Application Publication No. 59-74547, etc. In the present invention, Japanese Patent Application No. 58-516571, Japanese Unexamined Patent Publication No. 58-58
-189628, 58-193541, US Patent
No. 4,137,079, No. 4,168,980, etc.
The nitrogen-containing heterocyclic compound described in 5, especially containing a nitrogen atom
By containing an appropriate amount of a 6-membered or 6-membered heterocyclic compound
This is advantageous because it suppresses fog and accelerates development.
It is. In addition, mercaptan described in Japanese Patent Application No. 57-222247
It is also preferable to contain thiophenols and thiophenols. In the present invention, irradiation and halation can be prevented.
Special Publication Showa 4g-3692 to improve sharpness and sharpness.
Publications and U.S. Patent Nos. 3,252,921 and 2,527,58
No. 3, No. 2956879, etc.
light absorption by filter dyes, carbon black, etc.
Sexual substances can be incorporated into the material. Preferably, these dyes are thermally decolorizable.
are preferred, for example, US Pat. No. 3,769,019;
Described in No. 3745009 and No. 3615432
Preferably, such dyes are used. In addition, in the present invention, the image is activated at the same time as the development is activated.
Stabilizing compounds can be used. inside it
2-hydroxy as described in U.S. Pat. No. 3,301°678.
Substitute for ethyl isothiuronium trichloroacetate
- Intiuroniums, U.S. Pat. No. 3, 6
69. 1,8-(3,6-thioxaoctane) described in No. 670
Bis(inchuronium trichloroacetate) etc.
bisisothiuroniums. Thiolation as disclosed in West German Patent No. 2,162,714
compounds, 2-A described in U.S. Pat. No. 4,012,280
Mino-2-thiazolium trichloroacetate, 2-
Amino-5-bromoethyl-2-thiazolium tric
Thiazolium compounds such as loloacetate, US patent
Bis(2-amino-2-
thiazolium) methi, renbis(sulfonylacetate)
),? -Amino-2-thiazolium phenylrunyl
In 7, α-sulfonyl atom is used as an acidic moiety such as tate.
Compounds with Cetate, U.S. Pat. No. 4,088,4
2-carboxycarboxya as the acidic moiety described in No. 96
Compounds having mido are preferably used. Also, the trialli described in U.S. Pat. No. 4,411,985
phosphofurne compounds, No. 4,351.898 and
Menions 1 and 2 described in JP-A-57-154173
．． 4-) Liazolium-3-thousand oleate compounds are also useful.
be. 1 When using a dye-donating substance in the present invention, water release
Use of a compound is advantageous because it accelerates the dye release reaction. Water-releasing compounds are compounds that decompose and release water during thermal development.
It is a compound. These compounds are especially useful for fiber transfer
Known for textile printing, Japanese Patent No. 50-88386
NH4Fe (SO4)2 ・l 2H2 described in the published publication
0 etc. are useful. In the present invention, photographic light-sensitive materials and dye fixing materials include
, photographic emulsion layer and other binder layers are inorganic or organic.
It may contain a hardening agent. For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal,
geltaraldehyde, etc.), N-methylol compounds (
Dimethylol urea, methylol dimethyl hydantoin
etc.), dioxane derivatives (2,3-dihydroxydio
xane, etc.), activated vinyl compounds (1°3.5-tria
Chryloyl-hexahydro-8-triazine, 1,3-
(vinylsulfonyl-2-propanol, etc.), activated halo
Gen compound (2,4-dichloro-6-hydroxy-5-
) riazine, etc.), mucohalogen acids (mucochloric acid,
mucophenoxychloric acid, etc.) alone or in combination.
Can be used together. The photosensitive material used in the present invention has a woody colloid layer.
May contain UV absorbers, e.g. substituted with aryl groups
benzotriazole compound, 4-thiazolidonation
compound, benzophenone compound, cinnamic acid ester compound,
butadiene compounds, benzoxazole compounds, and
Ultraviolet absorbing polymers and the like can be used.
These UV absorbers are fixed in the hydrophilic colloid layer above.
may be done. Photographic emulsion of the present invention and photosensitive material made using the present invention
Coating aids may be added to the photographic emulsion layer or other hydrophilic colloid layer of the material.
agent, antistatic, improves slipperiness, emulsification and dispersion, prevents adhesion and
and improvement of photographic characteristics (e.g. development acceleration, contrast enhancement, sensitization), etc.
Various surfactants may be included for various purposes. For example, saponins (steroids), alkylene oxy
derivatives (e.g. polyethylene glycol, polyethylene
glycol/polypropylene glycol condensate, poly
Ethylene glycol alkyl ethers or polyethylene
Ren glycol alkyl aryl ethers, polyester
Styrene glycol esters, polyethylene glycol
Sorbitan esters, polyalkylene glycol alcohols
Kylamines or amides, silicone polyethylene
oxide adducts), glycidol derivatives (e.g.
Lukenyl succinic acid polyglyceride, alkylphenol
polyglycerides), fatty acid esters of polyhydric alcohols
Nonionic surfactants such as 1st class alkyl esters
;Alkyl carboxylate, alkyl sulfonate, alkyl carboxylate, alkyl sulfonate,
alkylbenzene sulfonate, alkylnaphthalene
sulfonates, alkyl sulfates, alkyl phosphorus
acid esters, N-acyl-N-furkyltaurines,
Sulfosuccinic acid esters, sulfoalkyl polyoxy
Ethylene alkylphenyl ethers, polyoxyethyl
carboxylic acids such as lenalkyleinates, etc.
group, sulfo group, phosphor group, sulfate ester group, phosphoric acid ester group
Anionic surfactants containing acidic groups such as tel groups; amino acids
, aminoalkyl sulfonic acids, aminoalkyl sulfuric acids
or phosphoric acid esters, alkyl betaines, amines
Amphoteric surfactants such as oxides; alkylamine salts
, aliphatic or aromatic quaternary ammonium salts, pyri
Heterocyclic quaternary ammonium such as zinium and imidazolium
Phosphonium salts and aliphatic or heterocyclic rings
cationic surfactants such as surfactants or sulfonium salts
can be used. Metal complexes are effective as anti-fading agents for dye images.
As the metal complex, a ligand selected from mono- to tetradentate ligands is used.
Preferred are chelate complexes having at least one
As a specific embodiment of the chelate complex, the bidentate ligand is 2
1 tridentate ligand and 1 monodentate ligand
one in which one tetradentate ligand is coordinated. Ligand atoms include nitrogen atoms and oxygen atoms. Sulfur atoms, halogen atoms (e.g. chlorine atoms, bromine atoms,
iodine atom) is preferred. The key metals in metal complexes are transition metals, that is, the number of atoms
From 21 Sc to 30 Zn. 39 (7) Y to 48 Cd, 57 f) La
From 80 Hg to 89 Ac or more atoms.
Among them, Cu is effective. Co, Ni, Pd, and Pt are preferred. Metal complexes form an anion as a whole complex (term group).
or is preferably electrically neutralized within the complex.
, when forming a metal complex anion, its counter cation
is preferably a mono- or divalent cation. Examples of mono- or divalent cations include alkali metal ions.
(Li◆, Ha◆, Ni◆), alkaline earth metal ions
(M g 2; ca ”, S r ”. Ba”), bisonium ion (bis ammonium
ions and bisphosphonium ions), onium ions (
Quaternary ammonium ion, quaternary phosphonium ion, 3
sulfonium ions), etc. Transition metal complexes themselves have an absorption maximum in the visible wavelength range.
Many of them are colored, but in colored cases, it is necessary to spray the dye fixing layer.
Since it will cause tint, it is included in one dye fixing layer.
The anti-fading agents used are not colorless, and most are colorless.
preferable. Colorless or almost colorless anti-fade agents are listed below.
General formulas (1-I), (2-I) to (2-IV), (3-
These are metal complexes represented by 1) and (3-II). (1-I) In the above formula (1-I), Ml is (u, co. Ni, Pd or Pt, X is O or S,
R11 is an alkyl group, an aryl group, an alkoxy group, or
nu, which represents an aryloxy group and is bonded to the same 1g member, is
They may be linked together to form a 6-membered ring with the P atom.
stomach. For more information on this metal complex, see U.S. Patent No. 4.241.
, No. 155 specification, columns 3 to 6,
Specific examples include the following compounds. In the above formulas (2-I) to (2-IV), M2 has the same meaning as M1
It is. R, R, R and R42 are each a hydrogen atom,
Halogen atoms, cyano groups, alkyl groups, aryl groups,
Represents a chloroalkyl group or a heterocyclic group, but these
Atoms or groups can be bonded directly or through divalent linking groups.
Bonds to the carbon atom of the Zen ring. R and R, R and R, or R32 and R42 are connected to each other.
may form a 6-membered ring. R52 and R82 are each a hydrogen atom, an alkyl group, or an ali
represents a group. R112 is a hydrogen atom, an alkyl group, or an aryl group. Or represents a hydroxyl group. R72 represents an alkyl group or an aryl group, Z is 5
Or represents a nonmetallic atomic group necessary to form a 6-membered ring. For more information on this metal complex, see U.S. Patent No. 4.245.
, No. 018 specification, columns 3 to 36.
, Specific examples include the following compounds. In the above formulas (3-I) and (3-11), M3 is general
It has the same meaning as Ml in formula (1-I), and R, R, R and
and R43 each have the same meaning as the general formula (2% formula % R. R and R83 each represent a hydrogen atom, an atom
Alkyl group, aryl group, acyl group, alkoxycarbonyl group
group, aryloxycarbonyl group, alkylsulfonyl group
group or arylsulfonyl group. For more information on this metal complex, see U.S. Patent No. 4.254.
, No. 195 specification, columns 3 to 8,
Specific examples include the following compounds. Other metal complexes that can be used as anti-fade agents are
Patent No. 4,050,938, Patent No. 4.241,154
No. 4,239,843, No. 4,242,43
No. 0, No. 4.242.431, No. 4,248,3
No. 29, No. 4,256,817, No. 4, 248
. No. 949, No. 4,246,330, No. 4.301
, No. 223, No. 4,242,429 and No. 4,
No. 343,886. Matting agent added to the protective layer of the material used in the present invention
A conventionally known one can be used. Matting agents are well known in the photographic field, and *
Inorganic or dispersible in an aqueous organic colloidal binder
It can be defined as a discrete solid particle of organic material. inorganic
Examples of matting agents include oxides (e.g. silicon dioxide,
titanium oxide, magnesium oxide, aluminum oxide, etc.)
, alkaline earth metal salts (e.g. sulfates and carbonates)
, specifically barium sulfate, calcium carbonate, and sulfate mag.
nesium, calcium carbonate, etc.) 1 Halo that does not form an image
Silver genide grains (silver chloride, silver bromide, etc. with additional halogen components)
A small amount of iodine atoms may be added as
Glass, etc. Examples of organic matting agents include starch and cellulose esters.
(e.g. cellulose acetate pyrovionate, etc.),
Cellulose ethers (e.g. ethylcellulose), synthetic
It is made of synthetic resin, etc. Examples of synthetic resins include water-insoluble or
is a dispersion of poorly soluble synthetic polymers, such as alkyl
(meth)acrylate, alkoxyalkyl (meth)acrylate
Acrylate, glycidyl (meth)acrylate, (meth)
) acrylamide, vinyl ester (e.g. vinyl acetate)
), acrylonitrile, olefins, styrene, etc.
alone or in combination, or with acrylic acid, meth
Acrylic acid, α, β-unsaturated dicarboxylic acid, hydroxya
alkyl (meth)acrylate, sulfoalkyl (meth)
Monomer combinations of acrylate, styrene sulfonic acid, etc.
Polymers used as body components can be used. in
Polymethyl methacrylate is also preferred. The average particle size of these matting agents is approximately 0°1 to 10I
L■ is appropriate, preferably 0.5 to 81Lm, and
Preferably 1 to 6 final layers. 1lIF, which contains a matting agent! ) thickness is
Approximately 1/10 to 1/1/1 of the average particle size (average diameter) of the agent
3 is preferable from the viewpoint of improving releasability. The protective layer may be multi-layered, in which case a matting agent
is contained in the outermost layer and has a two-layered configuration, e.g.
If oil droplets are dispersed in at least one layer of these layers,
is preferable. The appropriate size of the oil droplets is approximately 0.01 to 20 l.
．． 05 to 1 OIL Maro is preferred. The substance that forms these oil droplets is usually a photographic coupler.
High-boiling organic compounds used for dispersion of
This high boiling point organic compound has a boiling point of 180°C or higher at normal pressure.
The above are preferred, e.g. U.S. Pat. No. 2.322.0
Phthalic acid furkyl ester described in No. 27 (
dibutyl phthalate, dioctyl phthalate),
acid esters (diphenyl phosphate, triphenyl phosphate)
Ruphosphate, tricresyl phosphate, geo
(cutyl butyl phosphate), citric acid ester (e.g.
(e.g. acetyl tributyl citrate), benzoic acid ester
(e.g. octyl benzoate), alkylamides (e.g.
diethyl laurylamide), fatty acid esters (e.g.
dibutoxyethyl succinate, diethyl azelate)
, trimesic acid esters (e.g. trimesic acid tributate)
Chill), etc. As a slippery agent, high-grade alkyl sulfate soda, high-grade fat
Acid higher alcohol ester, carbowax, higher alcohol
Examples include kill phosphate esters and silicone compounds.
Ru. In particular, U.S. Patent No. 2,882,157;
No. 121.060, No. 3.850.640, JP-A-Sho
The compounds described in No. 51-141623 etc. are used alone or
It is particularly effective to use two or more kinds together. The appropriate amount of slip agent to be applied is approximately 5 to 20,067 m2.
Ru. The organic fluoro compound has at least three fluorine atoms and
linear or cyclic compounds containing at least 3 carbon atoms
including cationic, nonionic, anionic, solid
Any type of in-type can be preferably used. Typical organic fluoro compounds used in the present invention
See, for example, U.S. Pat. No. 3,589,906. Same No. 3,868,478, Same No. 3,754,924. Same No. 3,775,126. Same No. 3.850.840. British Patent No. 1.330.356, JP-A-51-
It is described in No. 108419. For representative examples of these organic fluoro compounds, please refer to
Described in columns 8 to 17 of Publication No. 57-9053
ing. Particularly preferred organic fluoro compounds include anionic organic compounds.
It is a fluorine surfactant. The amount of organic fluoro compound added depends on the amount of the protective layer to be applied.
0.1 to 500 mg, preferably 1 to 200 m
It is g. One layer for fixing the dye improves the light fastness of the transferred dye image.
An anti-fade agent may be included to prevent this fading.
Examples of color inhibitors include photographic antioxidants and ultraviolet rays.
Those used as absorbents are effective. Specific examples of antioxidants for photography include hindered phenol
[e.g. 2,6-di-1-butyl-4-methylphenate]
henol, 2,2'-butylidene-bis-(-8-t
art-butyl-4-methylphenol), 4.4'-
Thiobis(3-methyl-5-t-butyl-phenol)
etc.], phenyl-β-naphthylamine, N. N'-G set butyl p-7 enylene diamine,
Enothiazine %N, N'-diphenyl-p-phene
Nylenediamine, d,l-α-tocopherol, 2.5
-t-hexyl-4-methoxyphenol and 6.6
'-dihydroxy-4,4,4', 4', 7.
7'-hexamethyl-bis-2,2'-spirochroman
etc. can be mentioned. In addition, as ultraviolet absorbers, benzotriazoles [
For example, 2-(3',5'-ditershalyamyl-2'
-hydroxyphenyl)benzotriazole, 2-(2
'-Hydroxy-3',5'-ditertibutylph
phenyl)-5-chlorobenzotriazole, 2-(3'
. 5'-ditertibutyl-2-hydroxyphenyl)
Benzotriazole, 2-(2'-hydroxyphene)
2-(2'-hydroxy)benzotriazole, 2-(2'-hydroxy)
C-5'-methylphenyl)benzotriazole, 2-
(Hydroxy-5'-tert-butylphenyl)ben
zotriazole, etc.], benzophenones (e.g.
Droxy-4-methoxybenzophenone, 2,2'-di
Hydroxy-4-methoxybenzophenone, 2-hydro
xy-4-methoxy-2'-carboxybenzophenone
, 2-hydroxy-4-n-octoxybenzophenone
. 2.4-dihydroxybenzophenone, etc.), 2-ethyl
Hexyl-2-cyano-3,3'-diphenylacryle
p-octylphenyl salicylate, 1-(2,
4-di[-butylphenyl)-3,5-di-t-buty
Examples include ru-4-hydroxykyunzoate, etc.
Wear. There are two types of dye transfer for dye transfer from the photosensitive layer to the dye fixed layer.
Motion aids can be used. As a dye transfer aid
Dissolve the dye to be transferred at least in a heated state.
A liquid or hot solvent can be used. In other words, if the dye to be moved is a hydrophilic dye,
, using a hydrophilic liquid or a wood-philic heat solvent, and lipophilic dyes.
In the case of somen solvent that can dissolve it, oil is lipophilic.
A hot solvent or the like can be used. Also, the parent of the pigment
Depending on the degree of wood property and lipophilicity, wood-loving liquid and wood-loving hot melt
Mix appropriate amounts of agent, lipophilic solvent, and lipophilic heat solvent.
You can also be there. The dye transfer aid is used in one dye fixing layer or/and photosensitive layer, preferably
Preferably, it may be used by moistening the dye fixing layer with a solvent.
It can be directly included in this layer beforehand, or it can be
or adsorbed to crystals, as crystal water, or as a microorganism.
It may also be incorporated as a black capsule. The woody or lipophilic properties used as this dye transfer aid
Solvents include water, caustic soda, caustic potash, and soda carbonate.
Basic aqueous solutions containing inorganic alkali metal salts such as meth
Nol, ethanol, propatool, butanol, ben
Monohydric alcohol such as dialcohol, ethylene glycol
gelatin glycol, polyethylene glycol, polymer
Polyhydric alcohols such as lopylene glycol and glycerol
, furyl alcohol, methyl cellosolve, cellosolve
Ethers with alcoholic OH groups such as acetone,
Acetylacetone, methyl ethyl ketone, hexanone,
Ketones such as cyclohexanone, methyl acetate, ethyl acetate
butyl acetate, methyl benzoate, n-butyl phosphate, etc.
esters, diethylamine, dibutylamine, pyri
Nitrogen-containing solvents such as gin, +norin, etc. can be mentioned.
. In photosensitive materials in which the dye to be transferred is woody,
Adding dye transfer aids to photosensitive materials and/or dye fixing materials
When incorporated, this dye transfer aid is wood-philic.
by heating in the presence of a hot solvent.
Transferring this wood-loving pigment to a pigment fixing material and fixing it.
I can do it. One dye is fixed by heating in the presence of a wood-philic hot solvent.
In image forming methods in which mobile dyes are transferred to layers,
Even if migration starts at the same time as the release of a dye, the release of one dye
It may be after the completion, therefore, the addition for the move
Heat may be applied after heat development or at the same time as heat development.
It's okay. Heating for dye transfer is used to improve storage stability, workability, etc. of photosensitive materials.
From the viewpoint of 60°C to 250°C, the present invention
In this temperature range, it acts as a wood-philic heat solvent.
You can choose what works best for you. hydrophilic heat
The solvent helps the dye move quickly by heating.
Of course, it is necessary, but the heat resistance of photosensitive materials, etc.
If also taken into consideration, the melting point required for the wood-philic thermal solvent
is 40°C to 250°C, preferably 40°C to 200°C,
More preferably, the temperature is 40°C to 150°C. The wood-friendly heat solvent is in a solid state at room temperature,
A compound that becomes liquid when heated, (inorganic/
organic) value〉l, and water solubility at room temperature is 1 or more.
is defined as the compound above. Here inorganic and organic
is a concept for predicting the properties of compounds;
For details, see page 719 (195
7). As a wood-philic heat solvent,
It is an essential condition that the value (organicity/organicity) is 1 or more.
, preferably 2 or more. On the other hand, if we consider it from the perspective of molecular size, moving colors
There are parts around the element that can move on their own without hindering their movement.
It is considered preferable that children exist.゛ Therefore
, the molecular weight of the hydrophilic heat solvent is preferably small, about 20
Less than or equal to 0. A more preferred molecular weight is about 100 or less. □ Hydrophilic thermal solvent is a hydrophilic dye produced by heat development.
can substantially assist in the migration of dye to the dye fixing layer.
Since only one dye is required, five dyes can be contained in one dye fixing layer.
Not only that, it can also be included in the photosensitive material of the photosensitive layer.
It can be contained in both the fixed layer and the photosensitive layer, or
In the light-sensitive material or as an independent dye fixing layer with a dye fixing layer.
An independent layer containing a wood-philic heat solvent is provided in the fixed material.
You can also do that. Increases the efficiency of dye transfer to the dye fixing layer
From the perspective of
It is preferable to include it in/or an adjacent layer. Wood-philic thermal solvents are usually dissolved in water and dispersed into the binder.
However, alcohols such as methanol and ethanol
It can also be used by dissolving it in a solution such as a gel. Hydrophilic heat solvents that can be used include ureas, pyridine, etc.
ions, amides, sulfonamides, imides, alcohol
metals, oximes, and other heterocycles.
can. Specific examples of this wood-philic heat solvent and particularly preferred among them.
A preferred specific example is JP-A-58-42092 No. 1.
Compounds described on pages 49 to 158 can be mentioned.
Ru. This hydrophilic heat solvent can be used alone or in combination.
The above can also be used together. This wood-philic thermal solvent is used in photosensitive materials or dye-fixing materials.
1 of the amount calculated by weight of the total coating film thickness excluding the water-based hot solvent
0 to 300% by weight, preferably 20 to 200% by weight, especially
It is preferably used in the range of 30 to 150% by weight.
can. The image receiving layer in the present invention is a heat-developable color photosensitive layer.
There is a dye-fixing layer used in the material, and mordants are commonly used.
You can choose any agent from among them, but among them
Particularly preferred are polymeric mordants, where polymeric mordants
What is a drug? Polymers containing tertiary amino groups, nitrogen-containing heterocyclic moieties
Polymers containing these quaternary cation groups
Ma et al. The mordant used in the present invention has the general formula (LXI)
A tertiary amino group represented by ~(LXIV), or a quaternary
Polymer containing one unit of donyl monomer having a class ammonio group
Mar is preferred. General formula (LX I) [In the formula, R1 has a hydrogen atom or a current number of carbon atoms of 1 to 6]
represents a lower alkyl group, L is 1 to 20 carbon atoms
Represents a divalent linking group having a number of children, E is the number of carbon atoms
He contains a nitrogen atom as a constituent with a double bond with
Represents a telo ring, n is 0 or l. ] General formula (LXn) ■ (-CH2-C+ (L) n 4 R5 [In the formula, R, L, and n are the same as the general formula (LX■)
R4 and Rs are the same or different, respectively.
an alkyl group having carbon atoms on the 1-12 side of
7 to 20 (representing an aralkyl group having a carbon atom of Il)
However, R4 and R5 are interconnected to form a cyclic structure together with the nitrogen atom.
n is O or l. ] General formula (LXm) RI (-CH2-C+ (L) n ■ GΦXθ [In the formula, 11, L, and n are the same as in the general formula (LXI)
Go is quaternized and has a double bond with a carbon atom.
represents a heterocycle containing a nitrogen atom as a constituent component.
Was, X9 represents a monovalent anion, n is 0 or
or 1. ] General formula (LXIV) CH2-C) (L) n R4-Ne-Re Xe [In the formula, R1, L, and n are the same as in the general formula (LX I)
represents, R4 and R5 are the same as the general formula (LX■)
, Re is the same as R4 and R5.
selected from among. Xe is the same as the general formula (LXm)
represent something. R4, R5, R, are interconnected and form a ring together with a nitrogen atom.
may form a structure, n is 0 or l
. ] In the general formula (LXI) ~ (LXff), R1 is a hydrogen atom
Alternatively, a lower alkyl group having 1 to 6 carbon atoms 1 such as methyl
group, ethyl group, n-propyl group, n-butyl group, n-
7 Represents mil group, n-hexyl group, etc., and has a hydrogen atom
A methyl group is particularly preferred. L is one example of a divalent linking group having 1 to about 20 carbon atoms
For example, alkylene groups (e.g. methylene group, ethylene group,
limethylene group, hexamethylene group), phenylene group
(For example, O-7 enylene group, p-phenylene group 1m-phenyl group,
(e.g. phenylene group) 4arylene alkylene group (e.g.
NitoR2- or etc., where R2 is an alkylene group having 1 to about 12 carbon atoms
), -Go2 +, -co2-R3- (only
R3 is alkylene group, phenylene group, arylene group
), -CONH-R3- (where R
3 represents the same thing as above, ), R】 -CON-Ra- (However, R3 represents the same thing as above.
-co2-1- CON H-, -CO2-CH2CH
2-1-C02-CR2CR2C82-1-CONHC
H2-1-CONHCH2CH2+, -c ON H
CR2CR2CR2- and the like are particularly preferred. In general formula (LXI), E has a double bond with a carbon atom
Heterocycle containing a nitrogen atom as a constituent 1 e.g. imida
zole ring (eg, etc.), triazole ring (eg, etc.), pyrazole ring (eg, etc.), pyridine ring (eg, etc.). It represents a pyrimidine ring (such as, etc.), and an imidazole ring or a pyridine ring.
Particularly preferred. A bicarbonate having a tertiary amino group represented by the general formula (LXI)
Preferred specific examples of polymers containing one unit of
U.S. Pat. Nos. 4,282,305 and 4,115
, No. 124, No. 3.148,061, etc.
The following may be mentioned, including mordants: Even general formula (LXn) TeR4, Rs Hal ~12 charcoal
Alkyl group having an elementary atom 1 For example, an unsubstituted alkyl group (
Methyl group, ethyl group, n-propyl group, n-butyl group,
n-7 mil group, hexyl group, n-nonyl group, n-decyl group
groups, n-dodecyl groups, etc.), substituted alkyl groups (methoxy groups, etc.),
Ethyl group, 3-cyanopropyl group, ethoxycarbonyl group
ethyl group, acetoxyethyl group, hydroxyethyl group
, 2-butenyl group, etc.), or 7 to 20 carbons
Aralkyl group having atoms, e.g. unsubstituted aralkyl group
, (benzyl group, phenethyl group, diphenylmethyl group,
naphthylmethyl group, etc.), substituted aralkyl group (4-methyl group, etc.),
Tylbenzyl group, 4-isopropylbenzyl group, 4-methane
Toxybenzyl group, 4-(4-methoxyphenyl)base
3-chlorobenzyl group, 3-chlorobenzyl group, etc.)
. In addition, R4 and R5 are connected to each other to form a ring together with a nitrogen atom.
As an example of forming a structure, 1 represents a number, for example). Examples include. Bicarbonate having a tertiary amino group represented by the general formula (LXn)
Preferred specific examples of polymers containing one unit of nil monomer include
Examples include the following: (Number: mol%) In the general formula (LXm), G■ is quaternized and combined with carbon.
Heterocontaining a nitrogen atom with a double bond as a constituent
represents a ring, examples of which include imidazolium salts). triazolam salts (e.g., etc.), pyridinium salts (e.g., etc.), among which ichmidazolium salts, pyridinium salts, etc.
Particularly preferred are lysinium salts, where R4 is of the general formula (
Represents the same thing as LXn), and has a methyl group, ethyl group,
A ndyl group is particularly preferred. General formula (LXm), (LXIV)-c'Xe (with anion
For example, halogen ion (e.g. chloride ion)
, bromide ion, iodine ion), alkyl sulfate ion (
For example, methyl sulfate ion, ethyl sulfate ion), alkyl
or arylsulfonate ion (e.g. methane)
sulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p
-1 luenesulfonic acid), acetate ion, sulfate ion, etc.
Examples include chloride ion, p-1 luene sulfonate, etc.
Preferred is the acid ion. It has a quaternary ammonio group represented by the general formula (LXm)
Preferred specific examples of polymers containing one vinyl seven unit
as. British Patent No. 2,058,101, British Patent No. 2,093,041, British Patent No. 1,594,961, United States Patent No. 4,124,386, British Patent No. 4. l15, No. 124. The following are listed, including the mordants described in 4,273,853, 4,450,224, and JP-A-48-28225.
It will be done. Li1tcj +0I2-CI-)-N' P-7509, in the general formula (LXIV), R4 and R5 are connected to each other and
An example of forming a cyclic structure with a nitrogen atom is (where m represents an integer from 4 to 12), etc.
and an example in which a cyclic structure is formed by R,, R5, and R6.
For example, A quaternary ammonio group represented by the general formula (LXIV)
Preferred embodiments of polymers containing one vinyl monomer unit having
Examples include U.S. Patent No. 3.709.690;
, No. 898,088, No. 3,958,995, etc.
Including the mordants listed, the following may be mentioned: cte. CIe (number bimolar negative miscellaneous, U.S. Patent No. 2.548.564; U.S. Patent No. 2,484,430, U.S. Patent No. 3,148°061)
, disclosed in Specification No. 3,756,814, etc.
Vinylpyridine polymer. and vinylpyridinium cationic polymer; US patent
No. 3.625.694, No. 3,859.096,
No. 4,128,538, British Patent No. 1,277.4
Can be crosslinked with gelatin etc. disclosed in Specification No. 53 etc.
Polymeric mordants; US Pat. No. 3,958,995. Same No. 2,721.11152, Same No. 2,798゜06
No. 3, JP-A-54-115228, JP-A No. 54-1455
Disclosed in No. 29, Specification No. 54-126027, etc.
Aqueous sol type mordant; U.S. Patent No. 3,898,088
Water-insoluble mordants disclosed in U.S. Pat.
4. No. 168,976 (Unexamined Japanese Patent Publication No. 137333/1983)
Antibodies that can form covalent bonds with the dyes disclosed in the specification etc.
Responsive mordants: further U.S. Pat. No. 3,709,690;
3, 788, 855, 3,642,48
No. 2, No. 3 488.706, No. 3.557.0
No. 66, No. 3,271,147, No. 3,271.
No. 148, JP-A-50-71332. No. 53-30328, No. 52-155528, No. 5
No. 3-125 and No. 53-1024.
Examples include mordants. Others, U.S. Patent No. 2,675,316, U.S. Patent No. 2,8
Mention may also be made of the mordants described in No. 82,156.
Wear. The mixing ratio of the polymer mordant and gelatin of the present invention and the polymer
The amount of mordant applied depends on the amount of dye to be mordanted,
The type and composition of the mer mordant, as well as the image forming process used.
It can be easily determined by a person skilled in the art depending on the situation, etc.
The mordant/gelatin ratio is 20/80 to 80/20 (by weight)
ratio), mordant application amount is preferably 0.2 to 15 g/m2
Mordant, preferably used at 0.5g to 8g/m2
The molecular weight of the polymer used in the agent is preferably 1000.
~1000000, especially 10000~200000
Ru. When using the above polymer as a mordant in the present invention,
In some cases, metal ions are also used in photosensitive materials and dye fixing materials.
By this, the transfer density of the dye can be increased. This metal ion is present in the mordant layer containing the mordant or in the vicinity.
It is added to the upper and lower layers. metal used here
Ions are colorless and stable against heat and light.
Desirable, i.e. Cu2+, Zn2+, lti 1
2+, p j 2+, Pd2+, Co3+ ions, etc.
Polyvalent ions of transition metals are preferred, and Zn2+ is particularly preferred.
Preferably, this metal ion is usually in the form of a water-soluble compound
, for example ZnSO4, Zn(CH3CO2)2,
The amount added is 0,01~5 g/rn.
2, preferably 0.1 to 1.5 g/m2. In the present invention, as a heating method for development, conventionally known
Knowledgeable methods can be used. For example, if you are sensitive to a hot plate or drum such as a hot plate,
The optical material may be brought into contact with the material or transported using a heat roller.
You can also set In addition, air heated to high temperatures, high frequency heating, and
Heating can also be done with a laser beam. photosensitive material
In some cases, heating can also be done using an infrared heater.
Ru. Furthermore, by utilizing eddy currents generated by electromagnetic induction,
A method of heating can also be applied. In addition, liquids that are inert to the photosensitive material, such as fluorine
The system liquid may be heated in a heated bath. Furthermore, in addition to the heating means mentioned above, a heating source can also be used for photosensitive materials.
For example, carbon
A photosensitive material with a layer of conductive particles such as lac or graphite
It is placed inside and utilizes the Joule heat generated when electricity is applied.
It's okay. There are various patterns for heating the photosensitive material.
can be applied. The most common method is heating at a constant temperature.
However, depending on the characteristics of the photosensitive material, multi-stage heating, even
For example, it is effective to gradually lower the temperature after a short period of high temperature.
It is. Photosensitive materials are susceptible to air oxidation during heating.
If necessary, deaerate the area around the heating part or replace it with inert gas.
is valid. In addition, the surface of the photosensitive material can be directly connected to the heating area.
Photosensitive material that can be brought into contact or exposed to air
When developing with the surface of the material facing the air, the
Cover to prevent moisture and volatile components from evaporating and to retain heat.
It is also effective to attach . In the present invention, when using electrical heating as the developing means,
Transparent or opaque heating elements can be used as resistive heating elements.
It can be made using conventionally known techniques. As a resistance heating element, a thin film of an inorganic material that exhibits semiconductivity is used.
How to use it and the material in which conductive fine particles are dispersed in a binder.
There is a method using organic thin film. Used for the former method
Materials that can be used include silicon carbide, molybdenum silicide, and rubber.
Tank Chromemade, a chip used as a PTC thermistor.
Tan-ugly barium ceramics, tin oxide, zinc oxide, etc.
Yes, a transparent or opaque thin film is created using known methods.
be able to. In the latter method, fine metal particles, carbon
Conductive fine particles such as black and graphite are used in rubber and composite materials.
Dispersed in synthetic polymer gelatin to have desired temperature characteristics
You can make a resistor. These resistors require photosensitive
It may be in direct contact with the base material, or it may be in direct contact with the substrate, intermediate layer, etc.
The heat generating element and the photosensitive element may be separated by
An example of the positional relationship is shown below. Heat-generating element/support/photosensitive element support/heat-generating element/photosensitive element support/heat-generating element/intermediate layer/photosensitive element support/photosensitive element/heat-generating element support/photosensitive element/intermediate layer/heat-generating element heat-developable photosensitive material Image exposure light source for recording images to
As such, radiation including visible light can be used.
. An example of a light source commonly used for normal color printing
For example, in addition to tungsten lamps, mercury lamps, iodine lamps, etc.
halogen lamp, xenon lamp or laser light
source, CRT light source, fluorescent tube 1 light emitting diode (LED), etc.
Any variety of light sources can be used. Also, LCD (liquid crystal) and PLZT (lanthanum-doped
microsci using lead titanium zirconate).
A combination of a shutter array and a linear or planar light source
Exposure means can also be used. When using an LED as an exposure means, the LED
Reproduced as a color image because it is difficult to obtain light
For example, green light, red light, and infrared light can be used as LEDs.
The three types of light that are generated are used to expose the
Yellow, magenta, and cyan dyes from each photosensitive layer
The heat-developable photosensitive material can be designed to emit
, that is, the green-sensitive portion (layer) has yellow dye-donating properties.
The red-sensitive part (layer) is a magenta dye-donor.
The infrared sensitive part (layer) is a cyan dye-donating substance.
However, the LED
generation characteristics, spectral sensitivity characteristics of photosensitive materials, and photosensitive
The generation properties of materials are not necessarily limited to this combination.
Rather, various combinations are possible. As a method of exposing heat-developable photosensitive materials. For example, the following methods can be mentioned. The first
This method uses line images such as technical drawings or photographic images with gradation.
A method of using an original image such as a statue and contact printing over the original image.
be. In addition, images taken with a video camera, etc.
The electric signal of the image sent from the video station or the original image
It is read by a photodetector such as a phototube or COD, and then
Requires image signals stored in the memory of a computer, etc.
After performing so-called image processing, directly C
RT or FOT (fiber optics cathode ray)
tube) and place this image in close contact or with a lens.
It is also possible to form an image on a heat-developable photosensitive material and print it.
It is possible (for example, JP-A-52-148302). In addition, the above process can be performed by performing the following method.
LED or i-semiconductor laser light source, etc. depending on the image signal
control the light emission or modulate the laser beam, etc.
Operational exposure may be performed by performing the following steps. i) For example, JP-A-57-151933 or
As stated in Application No. 57-226555,
Light sources such as LEDs and semiconductor lasers are mounted on the disc-shaped rotor.
arranged in the circumferential direction, and as this rotor rotates, it rotates once
A method of operation by moving in the axial direction. ii) As is known in so-called scanners, etc.
First, the photosensitive material is wrapped around a drum, and the drum is rotated.
and whether a light source is provided or whether the light source is
The head whose light is guided by optical fiber etc. is connected to the drum.
A method of operation by moving in the direction of the axis of rotation. 1ii) Direct the light beam from a laser light source etc. to a galvanometer mirror.
- Vibrate the photosensitive material using a light deflector such as a one-turn polygon mirror.
Operate by moving the material perpendicular to the direction of change
Method. Furthermore, as described in Japanese Patent Application No. 58-142229,
Apply image signals to the liquid crystal in a matrix or array,
Exposure can also be performed by controlling the light from the light source.
Wear. A dye transfer aid (for example, water) is used in the photosensitive layer of a heat-developable photosensitive material.
and the dye-fixing layer of the dye-fixing material.
This is to promote the movement of one image, but in advance
, dye transfer to the photosensitive layer or the dye fixing layer, or both.
After applying a kinetic agent, overlap the two.
You can also do it. Adding a dye transfer aid to the photosensitive layer or dye fixing layer
For example, Japanese Patent Application Laid-Open No. 58-5590
Roller application method or wire as described in No. 7
Bar coating method, described in Japanese Patent Application No. 58-55908
Apply water to the dye-fixing material using a water-absorbing material such as
As described in the method, Japanese Patent Application No. 58-55906,
A bead is formed between the heat-developable photosensitive material and the dye-fixing material.
A method for adding a dye transfer aid, Japanese Patent Application No. 58-559
Water repellent roller and dye fixation as described in No. 10
Add a dye transfer aid by forming beads between the layers.
Method, other, dip method, extrusion method
, a method of applying by ejecting it as a jet from pores, a method of applying it as a jet,
Various methods, such as applying the pad in a compressed manner.
can be used. The dye transfer aid is described in Japanese Patent Application No. 58-37902.
You can measure the amount in advance and give it within the range, or give it in sufficient quantity.
After applying pressure with a roller, etc., it is squeezed.
Use by adjusting the amount by removing it or drying it by applying heat.
be able to. For example, a dye transfer aid may be added to a dye fixing material by the above method.
After applying the pigment, pass it between pressurized rollers to remove excess pigment.
After squeezing out the transfer aid. There is a method of overlapping a heat-developable photosensitive material. Heating means in the transfer process include passing between hot plates or heating.
Heating in contact with the plate (for example, JP-A-50-62835
No.), contact the heated drum or heated roller while rotating.
(e.g., Japanese Patent Publication No. 43-10791), in hot air
Heating by passing
No. 7), by passing it through an inert liquid kept at a constant temperature.
heating, other rollers, belts, or guide members
heating by aligning it with a heat source (for example,
No. 1983-2546), etc. can be used. Ma
Graphite and carbon black are used as pigment fixing materials.
Alternatively, layers of conductive materials such as metals are applied,
A current is passed through this conductive layer to heat it directly.
It's okay. The heating temperature applied in the transfer process is the same as that in the heat development process.
transfer is possible at temperatures ranging from
60℃ or higher, and 10℃ or higher than the temperature in the heat development process.
Lower temperatures are preferred. The heat-developable photosensitive material and the dye-fixing material are overlaid and brought into close contact.
The pressure when applying varies depending on the implementation and the materials used.
But, 0, I N100 Kg/C■2. preferred
For example, 1 to 50Kg/c is appropriate (for example,
(described in No. 58-55691). The means for applying pressure to both of the above is between the pair of rollers.
method, pressing method using a plate with good smoothness, etc.
, various methods can be used. Also, apply pressure
The temperature of the rollers and plate during heat development ranges from room temperature to
It can be used within a range of process temperatures. ■Specific effects of the invention According to the invention, the photosensitive material is subjected to imagewise exposure or after imagewise exposure.
At the same time water and base and/or base precursor
The diffusible dye produced or released by heating in the presence of
Because it is transferred to the dye fixing layer during heating for development,
Provides images with high dye density and low fog, and is quick
A simple image forming method can be obtained. ■ Specific Examples of the Invention One specific example of the present invention will be shown below to explain the present invention in further detail.
Explain in detail. Example 1 A method for preparing a benzotriazole silver emulsion will be described. 28 g of gelatin and 13.2 g of benzotriazole were dissolved in 300 mjL of water. This solution
The mixture was kept at 40°C and stirred. Add 17g of silver nitrate to this solution and add water.
A solution of 100ml was added over 2 minutes. Adjust the pH of this benzotriazole silver emulsion and
The excess salt was removed. After that, set the pH to 6.30.
A benzotriazole silver emulsion with a yield of 400g was obtained.
Ta. Describe how to make the silver halide emulsion for the 5th calendar and the 1st layer.
. A well-stirred gelatin aqueous solution (20 g of gelatin and sodium chloride in 1000 mL of water)
containing 3 g of sodium chloride and kept at 75°C).
600 ml of an aqueous solution containing aluminum and potassium bromide
and silver nitrate aqueous solution (0.59 mole of silver nitrate in 800 ml of water)
for 40 minutes at the same time.
Added in quantity. In this way, a unit with an average particle size of 0.401 Lm
A dispersed cubic silver chlorobromide emulsion (bromine 50 mol %) was prepared. After washing with water and desalting, 5 mg of sodium thiosulfate and 4-hydro
xy-6-methyl-1,3,3&. Add 20 mg of 7-chitrazaindene at 60°C.
Chemical sensitization was performed. The yield of emulsion was 600g.
Ta. Next, we will explain how to make a silver halide emulsion for the third layer. A well-stirred gelatin aqueous solution (gelatin 20 g and sodium chloride 3 in 100 100 O of water)
(containing g) and kept at 75℃) with sodium chloride.
600ml of an aqueous solution containing potassium bromide and silver nitrate
Aqueous solution (dissolve 0.59 mol of silver nitrate in 600 m of water)
) were simultaneously added at equal flow rates over 40 minutes.
. In this way, monodisperse particles with an average particle size of 0.35 pm
A cubic silver chlorobromide emulsion (80 mol% bromine) was prepared. After washing with water and desalting, add 5 mg of sodium thiosulfate and
Droxy-6-methyl-1,3,3a. Add 20 mg of 7-chitrazaindene at 60°C.
Chemical sensitization was performed. The yield of emulsion was 600g.
Ta. Next, we will explain how to make a gelatin dispersion of a dye-donating substance.
I will explain. 5g of yellow dye-donating substance (A), surfactant and
succinic acid-2-ethyl-hexyl ester sulfonate
triisononyl phosphate, 5g, triisononyl phosphate
Weigh out 10 g, add 30 mJl of ethyl acetate, and add about 60 mJl of ethyl acetate.
The mixture was heated and dissolved at ℃ to form a homogeneous solution. This solution and stone
100 g of a 10% solution of ash-treated gelatin was stirred and mixed.
After that, use a homogenizer for 10 minutes at 110,000 rpm.
Dispersed. This dispersion is mixed with a yellow dye-providing substance.
It is called a dispersion. Using magenta dye-donating substance CB) and high boiling point solvent
Except for using 7.5g of tricresyl phosphate as
is a magenta dye-donor using the same method as above.
made a quality dispersion. Cyan dye is provided in the same manner as the yellow dye dispersion.
It was made using a sexual substance (C). As a result, color photosensitive materials with a multilayer structure as shown in the table below are produced.
made. Dye-donating substances (A) (B) (C) (D-1) (D-2) (D-3) Next, we will describe how to make the five dye-fixing materials. Poly(methyl acrylate-N,N,N-trimethyl
-N-vinylbenzylammonium chloride) (acrylic
Methyl lylate and vinylbenzylammonium chloride
The ratio is 1:l) 10g is dissolved in 200m of water, 1
It was uniformly mixed with 100 g of 0% lime-treated gelatin. child
Laminate the mixed solution with polyethylene in which titanium dioxide is dispersed.
An even wet film thickness of 901 L was applied to the coated paper support.
It was applied all at once. Furthermore, on top of this, 6 g of the base shown in Table 1, 16 m of water, 10
% gelatin 20g, 2-dithylhexyl succinate
4.8 ml of a 1% aqueous solution of sodium stealth sulfonate, 2.
2% of 4-dichloro-6-hydroxy-8-triazine
Mix and dissolve 2mJl of aqueous solution and add 30l of wet solution.
A dye fixing material (D
-1 to D-4). Tungsten light bulbs are used in the multilayered color photosensitive material mentioned above.
G, R1TR three-color separation with continuously changing density
Filter (G is 500-600 nm, R is 600-7
00nm bandpass filter, IR is 700n
(constructed using a filter that transmits more than 5 m),
Exposure was performed for 1 second at 00 lux. 20ml/m on the emulsion surface of this exposed light-sensitive material
2. Supply water with a wire bar, then add dye fixing material.
Overlap D-1, D-2, and D-4 so that the membrane surfaces are in contact with each other.
Ta. Heat the membrane so that the temperature of the water-absorbed membrane is 90 to 95℃.
After heating for 20 seconds using a temperature-adjusted heat roller
When the dye-fixing material is peeled off from the light-sensitive material, the
Yellow corresponds to G, RlIR three-color separation filter.
-, magenta, and cyan clear images were obtained. of each color
Maximum density (Dmax) and minimum density (Dmin)
Measured using a reflection densitometer (RD-519)
The results shown in Table 1 were obtained. Dye fixing material D-3 was heated in advance at 120°C.
After heating for 60 seconds with a heat roller, perform the same treatment as above.
The results shown in Table 1 were obtained. From the above results, the method of the present invention has a sufficient concentration and low power.
It turns out that a yellowtail statue can be obtained. Example 2 A method of making a dye fixing material will be described. Poly(methyl acrylate-N,N,N-trimethyl
-N-vinylbenzylammonium chloride) (acrylic
Methyl lylate and vinylbenzylammonium chloride
The ratio is 1:l) 10g is dissolved in 200mM water, l
Uniformly mixed with 0% lime-treated gelatin IQOg. child
Laminate the mixed solution with polyethylene in which titanium dioxide is dispersed.
A wet film thickness of 901L was applied to the coated paper support.
It was applied all at once. After drying this sample, the color with mordant layer
Used as elementary fixing material D-5. After exposing the light-sensitive material of Example 1, the dye fixing material was coated with 0.
Wipe 20 ml/m of 1N Possibility Solution
Applied with a coating, the film surface comes into contact with the exposed photosensitive material.
They were superimposed like this. After that, the same operations and treatments as in Example 1 were performed to obtain the first-order result.
I got results. Color Image Maximum density Minimum density Yellow - 2.0
0.13 magenta 2.85 0
．． 18 cyan 1.70
Based on the result of 0.17 or more, the base is incorporated into the dye fixing sheet.
It has been shown that there is no difference in effectiveness even when supplied externally.
It was done. Example 3 Preparation of benzotriazole silver emulsion containing photosensitive silver bromide 6.5 g of benzotriazole and 10 g of gelatin were mixed with 10 g of water.
Dissolved in 0100O. Keep this solution at 50℃ and stir
Stirred. Next, dissolve 8.5g of silver nitrate in 100ml of water.
The solution was added to the above solution over a period of 2 minutes. Next, 1.2 g of potassium bromide was dissolved in 50 mjL of water.
The liquid was added over 2 minutes. Prepared milk. after that,
The pH of the emulsion was adjusted to 6.0. Yield is 200g
It was. Preparation method of gelatin dispersion of dye-donating substance Color of the following structure
10g of a donor substance, 2-ethylhexyl succinate as a surfactant.
Stealth sulfonic acid sodium 0.5g,) leak resilfo
Weigh 4 g of sphate (TPO) and
Add 20mJl of water. The mixture was heated and dissolved at about 60°C to form a uniform solution. This solution and 100 g of a 10% solution of lime-treated gelatin were combined.
After stirring and mixing, use a homogenizer for 10 minutes at 1100
Dispersion was carried out at 00 rpm. Next, a method for preparing a photosensitive coating will be described. (a) Penzotriazole silver emulsion containing photosensitive silver bromide
10g (b) Dispersion of dye-donating substance 3.5g (C) Zella
Chin (10% aqueous solution) 5g (d) 2,6-dic
0.2g of lolo-4-aminephenol and 2m of methanol
Solution dissolved in Jl (e) 10% aqueous solution m1 of a compound with the following structure C9Hle 00 (CH2CH20) a H or more
After mixing (a) to (e) and heating and melting, a thickness of 18
3 on 0#Lm polyethylene terephthalate film
It was applied to a wet film thickness of 0.07 zm. Furthermore, the following composition was applied as a protective layer thereon. B) Gelatin 10% aqueous solution 30 mjL) Water
60mjL c) 2.4-dichloro
-hydroxy-3-) riazine 2%
Pour the mixed solution of 5ml a) to c) into a 301Lm wafer.
A light-sensitive material was prepared by applying the film to a thin film thickness and drying it. Using this photosensitive material and a tungsten light bulb, it was
imagewise exposure for 10 seconds. After that, using the dye fixing material D-1 of Example 1,
When the same processing and operations as in Example 1 were performed, the following results were obtained.
Ta. Maximum concentration 1.95 Minimum concentration 0.16 Example 4 Preparation of gelatin dispersion of dye-providing substance
Reducing dye release agent 5g, 61 CJ 2-ethyl-hexyl tosuccinate sulfonate
0.5g, ) Liegresyl phosphate (TCP
), add 20 ml of cyclohexanone to 10 g, and add about 60 ml of cyclohexanone.
It was heated and dissolved at ℃. This solution and the lθ% solution of gelatin
After stirring and mixing 100g of liquid, use a homogenizer to
Dispersion was performed at 110,000 rpm for 1 minute. Next, a method for preparing a photosensitive coating liquid will be described. (a) Benzotriazole silver emulsion containing photosensitive silver bromide (
(described in Example 3) 0 g (b) Dispersion of dye-providing substance 3.5 g (C) Next
1.5 mjL of 5% aqueous solution of the compound shown above (a
) to (C) are mixed and heated to melt, then polyethylene
Wet film thickness of 30 JLm on terephthalate film
was applied and dried. Furthermore, on top of this, a protective layer with a primary composition of 30%
Apply to a wet film thickness of 1Lm and dry to remove the photosensitive material.
Created. b) Gelatin (10% aqueous solution) 30g mouth) 2.4-
Dichloro-6-hydroxy-S-triazine 2% water soluble
Liquid 5mJL c) Water 70m
Regarding this photosensitive material, using a tungsten bulb, 2
Imagewise exposure was made for 10 seconds at 000 lux. Using dye fixing material D-1 of Example 1, the same procedure as Example 1 was carried out.
Similar operations and treatments were performed, and the following results were obtained. Maximum concentration l. 88 Minimum concentration 0020 Example 5 The following was applied on a polyethylene terephthalate film support.
A photosensitive material was prepared by applying the layers in the order listed. 1) Silver benzotriazole (0.62g/m in silver amount)
2), red-sensitive silver iodobromide (silver amount 1.42 g/m2
), dye developer compound example 5A (0.52 g/m2)
, gelatin (4,25 g/m2), represented by structure W
Auxiliary developer (0,11 g/m2), represented by structure X
Antifoggant (0.20 g/m2), compound of structure Y (0.40 g/m2)
m2), a compound represented by structure Z (0.95 g/m2)
) and tricresyl phosphate (0,90 g/m
2) layer containing 2) gelatin (1,2 g/m2) 3) silver benzotriazole (0.62 g/m2 in amount of silver)
2), green-sensitive silver iodobromide (silver amount 1.14 g/m2)
), Dye developer compound example (5B) (0.48g/
m2), gelatin (3,36g/m2), structure W
Auxiliary developer (0,11g/m2) expressed as
Antifoggant represented by Formula X (0.20g/xn
2), compound represented by structure Y (0.38g/m2
), a compound represented by structure Z (0.72 g/m2)
and tricresyl phosphini) (0,60 g/m2
) Calendar 4) Calendar containing gelatin (1,6 g/m2) Calendar 5) Benzotriazole silver (0.45 g/m2 in silver content)
2) Blue-sensitive silver iodobromide (silver amount 0.90g/m2)
), dye developer compound example (5C) (0.28 g/m2
), gelatin (2,85 g/m2), structure w-t'
auxiliary developer (0,10g7m2), represented by structure
antifoggant (0,17 g/m2), represented by structure Y
Hot solvent (0.36g/m2), represented by structure Z
Compounds to be washed (0,80g/m2) and tricresi
Layer 6) Containing Ruphosphate (0,50 g/m2) Note) (1) Containing Gelatin (1,8 g/m2)
) Auxiliary developer (Structure W) (2) Antifoggant (Structure X) (3) Surfactant (Structure Y) (9His <> 0CCH2CH20) a H (0
Compound (Structure Z) A tungsten light bulb is used in the color photosensitive material with the above multilayer structure.
Three-color separation of B, G, and H whose density changes continuously
Exposure for 1 second at 2000 lux through a filter
. Thereafter, using the dye fixing material D-1 of Example 1,
Perform the same operations and processing as in 1 and get the results shown in Table 2.
Obtained. Table 2 Using the methods and materials of the present invention according to the above examples.
It has been strongly demonstrated that clear images can be obtained. Example 6 A method for preparing an emulsion for the first layer will be described. A well-stirred gelatin aqueous solution (20 g of gelatin and 3 g of sodium chloride in 1000 d of water)
containing sodium chloride and potassium bromide (preserved at 75°C).
600 d of aqueous solution containing lium and silver nitrate aqueous solution (
0.59 mol of silver nitrate dissolved in 600 d of water)
Additions were made simultaneously at equal flow rates over 40 minutes. This way
Monodisperse cubic salt odor with average particle size o, 3sg
A silveride emulsion (80 mol% bromine) was prepared. After washing with water and desalting, 5 g of sodium thiosulfate and 4-hydroxy
C-6-methyl-1,3,3a,7-chitrazaindene
Chemical sensitization was performed at 60° C. by adding 20 mg. milk
The yield of the agent was 600 g. Next, I will talk about how to make the emulsion for the third layer. A well-stirred gelatin aqueous solution (20 g of gelatin and 3 g of sodium chloride in 1000 d of water)
containing sodium chloride and potassium bromide (preserved at 75°C).
Aqueous solution containing 600- and silver nitrate solution (
0.59 mol of silver nitrate dissolved in 600 dl of water)
and the following dye solution (I) at the same time for 40 minutes.
and added at equal flow rates. In this way the average particle size
Monodisperse cubic silver chlorobromide with 0.351L of dye adsorbed
An emulsion (80 mol % bromine) was prepared. After washing with water and desalting, 5 mg of sodium 100sulfate and 4-hydroxy
C-6-methyl-1,3,3a,7-chitrazaindene
Chemical sensitization was carried out at 60° C. by adding 20 μg. milk
The yield of the agent was 600 g. Dye bath solution (I) Methanol 400ml
Next, we will explain how to make a silver halide emulsion for the fifth calendar. A well-stirred gelatin aqueous solution (dissolve 20 g of gelatin and ammonia in 1000 d of water)
(kept at 50°C), potassium iodide and potassium bromide
An aqueous solution containing 100% of silver nitrate and an aqueous solution of silver nitrate (100% of water)
(1 mole of silver nitrate dissolved in 000d) at the same time.
was added while keeping pag constant. In this way
Monodisperse silver iodobromide octahedral emulsion with average grain size o, sg (
5 mol% of iodine) was prepared. After washing with water and desalting, chloroauric acid (tetrahydrate) 5B and sodium thiosulfate
Gold and sulfur sensitization was performed at 60°C with the addition of 2 mg of aluminum.
did. The yield of emulsion was 1.0 kg. In addition, benzotriazole silver emulsion and dye-donating substances
A gelatin dispersion was prepared in the same manner as in Example 1. These allow us to create color photosensitive materials with a multilayer structure as shown in the table below.
Had made. Tungsten light bulbs are used in the multilayered color photosensitive material mentioned above.
Three-color separation of B, G, and H whose density changes continuously
Exposure was made through the filter at 2000 lux for 1 second. Wash the emulsion side of this exposed light-sensitive material with 20-/g water.
Ear bar and then dye fixing material D of Example 1
-1, and were superimposed so that the film surfaces were in contact with each other. the
After that, the same processing and operations as in Example 1 were performed to obtain the first-order results.
Ta. Three-color separation Color Image Maximum density Minimum density
Filter B Yellow 1.95 0.15 2
．． 0G Magenta 2.20 0.13
2.5R cyan 2.25 0.14 2.5γ book:
Concentration difference implementation for 10 times the 5 exposure amount difference in the straight line part
Example 7 The emulsion of Example 1, the dispersion of dye-providing substance, and the sensitizing dye were
A photosensitive material with the structure shown in the table below was made using the following method. Example 1
Using the dye fixing material D-1 of
After the operation and processing, the following results were obtained. Color Image Highest density Lowest density Yellow
1.95 0.11 Magenta 1,75
0.08 cyan 1.70 0.09 Example 8 A method of preparing a silver halide emulsion for the first layer will be described. Emulsion (I) Well-stirred gelatin aqueous solution (gelatin 20g and sodium chloride 2 in 1000all water)
Potassium bromide (dissolved and kept at 75℃)
600ml of an aqueous solution containing 56g of alcohol and 7g of sodium chloride
Q and silver nitrate aqueous solution (0.59 mol of silver nitrate in 600 d of water)
(dissolved) was added at the same time over 60 minutes at the same flow rate.
did. After washing with water and desalting, add 40 g of gelatin and 200 g of water.
Adjust the pH by adding sodium thiosulfate and 4-hydroxy
C-6-methyl-1,3,3a. Optimal chemical sensitization using 7-chitrazaindene
, hexahedral monodisperse emulsion (1) with an average grain size of 0.4 JL, 700
I got g. Emulsion CU) Add a well-stirred gelatin aqueous solution (20 g of gelatin, 8 g and 0.01 g of sodium chloride dissolved in 1000 d of water and kept at 55°C).
Contains 35g of potassium bromide and 17.5g of sodium chloride.
6ool of aqueous solution! and silver nitrate aqueous solution (nitrogen in 600ml of water)
(dissolved 0.59 mole of acid silver) at the same time at equal flow rate.
Added over 60 minutes. 40g gelatin after washing and desalting
Add 200 d of water to adjust the pH, and add triethylthiourine.
The average
700g of hexahedral monodisperse emulsion (II) with a particle size of 0.57t
Obtained. Emulsion (m) Prepare emulsions (A) and (B) according to the following recipe and aliquot them in half.
The two were mixed to form an emulsion Cm). A. A well-stirred aqueous gelatin solution (20 g of gelatin, 8 g of sodium chloride, and 0.01 g of CH3 dissolved in 1000 d of water and kept warm at 50°C) has an odor.
An aqueous solution containing 35 g of potassium chloride and a silver nitrate aqueous solution
(0.29 mol of silver nitrate dissolved in 300 m of water)
) were simultaneously added at equal flow rates over 20 minutes. 1 more
After 0 minutes, 18g of potassium bromide and 9g of sodium chloride
300 d of aqueous solution containing silver nitrate and silver nitrate aqueous solution (in 300 d of water)
0.3 mol of silver nitrate was dissolved at the same time in equal amounts.
The mixture was added over a period of 20 minutes. Gelatin 40 after washing and desalting
Add 200 g of water and adjust the pH, and add triethylthio
Urea and 4-hydroxy-6-methyl-Otori 3,3a. Optimal chemical sensitization using 7-chitrazaindene
, hexahedral monodispersed emulsion (A) 70 with an average grain size of 0.351L
Obtained 0g. B ・ ・ Keep the gelatin aqueous solution at a temperature of 35°C during the first half of addition.
Exactly the same as emulsion (A) except that the interval was changed to 5 minutes,
700g of hexahedral monodispersed emulsion (B) with an average grain size of 0.15p
I got it. Emulsion (IV) A well-stirred gelatin aqueous solution (20 g of gelatin and lo(CH2) 25(CH2) 25CCH2 in water 10001II) 2
0H0.5g was dissolved and kept at 50℃).
Aqueous solution containing 69 g of potassium bromide and 2 g of potassium iodide
and silver nitrate aqueous solution (0.59 mol of silver nitrate in 600 ml of water)
pAg 8 ,
It was added while keeping the temperature at 0. 40g gelatin after washing and desalting
Adjust the pH by adding 200 Id of water and dilute with sodium thiosulfate.
Optimum chemical sensitization was carried out using
700 g of a 5JL hexahedral monodispersed emulsion (IV) was obtained. Emulsion (V) Same as emulsion (IV) except for keeping pag at 9.2 during addition.
Similarly, an octahedral monodisperse emulsion (V
) 700g was obtained. The method of making the silver halide emulsion for the third layer will be described. Emulsion (Vl) Prepare emulsions A) and B) according to the following recipe and mix in half each.
This was made into an emulsion (Vl). In a beaker containing 600 Ili of water, 20 g of gelatin,
1.2 g of potassium bromide and 6 cc of 25% aqueous ammonia
and stirred to dissolve. Keep this solution at 50℃
A solution of 100 g of silver nitrate dissolved in 600 d of water and an odor.
116 g of potassium iodide and 4 g of potassium iodide in 1000 g of water
Condroldo Double Jet
Add in 50 minutes while keeping the pag of the liquid at 8.9.
did. At that time, start adding the halogen solution and silver nitrate solution.
At the same time, add 0.15 g of the following dye (A) to 75 g of methanol.
Dissolve the entire volume in 25 minutes, starting with the addition of saliva.
Added. Pigment (A) After washing with water and desalting, add 20g of gelatin and 1001ft of water.
Adjust pH and add potassium bromide to bring PAg to 9.3.
did. Optimal chemical amplification is then performed using sodium thiosulfate.
The particle size was 0°51L and potato-shaped particles were obtained.
700 g of a black-sensitized silver iodobromide emulsion (A) was obtained. Furthermore, the 25% ammonia water used at the beginning is 2.5cc.
An otherwise identical emulsion (B) was also obtained. in this case,
Particle size was 0.31L. Emulsion (■) In a beaker containing 600 g of water, 20 g of gelatin, bromide
1.2 g of potassium and HO-C-CH2+25 +CH2+29 (-CH2
5 g of +20HO was added and dissolved with stirring. This solution
Dye (A) used in emulsion (Vl) 0.1 kept at 60°C
The residue obtained by dissolving 5g in methanol 75d and the following color
Dissolve 0.05g of element (B) in 125cc of methanol
The liquid was added. Next, add a long silver nitrate to 600 d of water.
Dissolved liquid and 64g of potassium bromide and potassium iodide
10g dissolved in 600d of water was added over 50 minutes.
did. After washing with water and desalting, add 20g of gelatin and 100ml of water.
Adjust H and add potassium bromide to make PAg 8.5.
Ta. Next, sodium thiosulfate and 4-hydroxy-6-
Methyl-1,3,3a. Optimal chemical sensitization using 7-chitrazaindene
Particle size 0.34, potato-shaped panchromatic sensitized odor
700 g of silver oxide emulsion (■) was obtained. Dye (B) Emulsion (■) In a beaker containing 600 d of water, 20 g of gelatin, bromide
Add 1.2 g of potassium and 25% ammonia water Scc.
The mixture was stirred and dissolved. This solution was kept at 50°C and the emulsion (V
0.30 g of the dye (A) used in step 1) was added to 150 g of methanol.
Add the solution dissolved in aQ and add 100g of silver nitrate first.
A solution dissolved in 600 g of water and 113 g of potassium bromide
and 8 g of potassium iodide dissolved in 1000 d of water.
Liquid pag is 8.2 using the Chondral double jet method.
The mixture was added over a period of 50 minutes while maintaining the temperature. After washing with water and desalting, add 20g of gelatin and 100d of water to pH.
was adjusted and potassium bromide was added to make PAg 8.5.
. Next, use sodium thiosulfate and chloroauric acid to optimize
Chemical sensitization was performed to obtain a particle size of 0.51L and a cubic pattern.
700 g of a cross-sensitized silver iodobromide emulsion (VIE) was obtained. Emulsion (IX) 20g gelatin in a beaker containing 800d water NaCl
Add 2g of aluminum and a 1% solution of the following compound and stir to dissolve.
I let it happen. H3 Keep this solution at 75°C and add the dye (A) used in emulsion (91).
)0.2g dissolved in 1oOcc of methanol was added.
I got it. Next, dissolve silver nitrate in 600++ dl of water.
solution, potassium bromide 56g and sodium chloride 7
g dissolved in 600 d of water was added over 40 minutes.
. After washing with water and desalting, add 20g of gelatin and 100d of water to pH.
Adjust pAg to 7.8 by adding sodium chloride.
Ta. Next, use 3-ethylthiourea and nucleic acid decomposition product to optimize
Panchromatic sensitized chlorbromide with a yield of 700g by chemical sensitization of
A silver emulsion (IX) was obtained. Particle size is 0.4 l and cubic
This section describes how to make the emulsion for the fifth layer. Emulsion (X) is prepared by combining emulsions (A) and (B) according to the following formulation.
The emulsion (X) was prepared and mixed in half amounts at a time. A. A well-stirred gelatin aqueous solution (20 g of gelatin and 2 g of sodium chloride in 1000 d of water)
(dissolved and kept at 60℃), potassium bromide and
Contains sodium chloride (0.59 mol in total) water-soluble
solution 600- and an aqueous solution containing 0.59 mol of silver nitrate 600-
Br8 was added at the same time over 25 minutes at the same flow rate.
At 0 mol%, the size is 0.25. Cubic monodisperse silver chlorobromide
created particles. At this time, at the same time as the start of silver halide grain formation.
At the same time, add 0.16 g of the following dye (I) to 400 c of methanol.
Add the solution dissolved in c to the gelatin aqueous solution over 15 minutes.
did. After washing with water and desalting, add 40 g of gelatin and 200 g of water to adjust the pH.
Sodium thiosulfate, chloroauric acid and 4-hydro
xy-6-methyl-1,3゜3a,7-chitrazainde
Optimal chemical sensitization was performed using a The yield of emulsion is 700 g. Milk B - A well-stirred gelatin aqueous solution (20 g of gelatin and 2 ml of sodium chloride in 100,011 l of water)
g and compound ^ dissolved in 0.015 g and kept warm at 75℃).
Contains potassium chloride and sodium chloride (total 0.5
9 mol) aqueous solution 600111I and 0.59 mol silver nitrate
800all of an aqueous solution containing B was added over 60 minutes.
Cubic monodisperse salt with r80 mol% and size O, SJL
Silver bromide particles were made. At this time, silver halide grain formation is initiated.
At the same time, add 0.16 g of the same dye (I) as emulsion (A).
Make gelatin by adding the solution dissolved in 400cc of tanol for 30 minutes.
was added to the aqueous solution. 40g gelatin after washing and desalting
Add 200 IllI of water to adjust the pH, and add triethyl
Perform optimal chemical sensitization using thiourea and nucleic acid digests.
Ta. The yield of emulsion is 700 g. Emulsion (X[) A well-stirred gelatin aqueous solution (20 g of gelatin and 10 g of sodium chloride in 1000 d of water
(dissolved and kept at 75℃) and potassium bromide
and sodium chloride (0.59 mol in total) water
solution 800d and an aqueous solution containing 0.59 mol silver nitrate 80
0d was added over 60 minutes to make the average particles at 55 mol% Br.
The size is 0.65. Cubic silver chlorobromide particles were prepared. At that time, 0.16 g of dye (II) was added 5 minutes before the start of particle formation.
A dye solution dissolved in 160 cc of methanol is added to gelatin.
Added to aqueous solution. After washing with water and desalting, add 40g of gelatin and 200Iall of water.
Adjust the pH using sodium thiosulfate and nucleic acid decomposition product.
Optimal chemical sensitization was performed using The yield of emulsion is 700 g. Dye (n) Emulsion OI) A well-stirred gelatin aqueous solution (gelatin in 600 ml of water)
Chin 20g and KBro, 5g and HO (CM 2 )
25CCH2) 25CCH2) 20H0,25g
(dissolved and kept at 75℃) and potassium bromide 14
．． Aqueous solution (1 liquid) containing 2g of potassium iodide and 0.2g of potassium iodide
Aqueous solution containing 160d and 0.12 mol of silver nitrate (■liquid)
1601d was added over 20 minutes. Leave it for 2 minutes
Contains potassium bromide and potassium iodide.
Aqueous solution (M liquid) 450111 and silver nitrate 0.47 mol
Contains an aqueous solution (■ liquid) at 45° for 30 minutes.
PAg is added using the cold double jet method while keeping it constant.
, the iodine content is 2 mol% and the average particle size is 0.5jL.
cubic silver iodobromide grains were prepared. (I) Liquid and (■)
Emulsion (X) is added at the same time as the liquid is added to start grain formation.
0.16g of dye (I) used in 400cc of methanol
Start adding the dye solution dissolved in
Added in quantity. After washing with water and desalting, add 40 g of gelatin and 200 d of water to adjust the pH.
Sodium thiosulfate, chloroauric acid and 4-hydro
xy-6-methyl-1,3゜3a,7-chitrazainde
Optimal chemical sensitization was performed using a The yield of emulsion is 700 g. Emulsion OI) A well-stirred gelatin aqueous solution (gelatin in 600ml of water)
20g of Chin, 2.5g of KBr and 0.08g of the compound were dissolved and kept at 75°C).
Water containing 14.2 g of potassium and 0.2 g of potassium iodide
Solution (■liquid) 160d and water containing 0.12 mol of silver nitrate
Solution (■ solution) 160- was added over 20 minutes. 2 minutes
After leaving it for a while, add potassium bromide and potassium iodide.
450all of an aqueous solution (M solution) containing silver and 0.0ml of silver nitrate.
Apply an aqueous solution (■ liquid) containing 47 moles of 450 soap for 30 minutes.
The pag was kept constant using the Chondral double jet method.
was added with an iodine content of 5 mol% and an average particle size of 0.
．． Five-island dodecahedral silver iodobromide grains were produced. When starting particle formation by adding liquid (I) and liquid (■)
At the same time, add 0.16 g of dye (II) used in emulsion (X[).
Add the dye solution dissolved in 300cc of methanol.
The mixture was added at equal flow rates over a period of 30 minutes. After washing with water and desalting, add 40 g of gelatin and 200 g of water to adjust the pH.
Optimized using sodium thiosulfate and chloroauric acid
chemically sensitized. The yield of emulsion is 700 g. Emulsions (1) to (1) above, dye-donating substance of Example 1
A photosensitive material having the structure shown in Table 3 was prepared using the dispersion. Using the dye fixing material D-1 of Example 1,
Similar operations and processing were performed to obtain the results shown in Table 4.
Obtained. Moreover, using the benzotriazole silver emulsion of Example 1,
A photosensitive material having the structure shown in Table 5 was prepared in the same manner as described above, and D of Example 1 was prepared.
The same procedure as in Example 1 was carried out using the dye-fixing material of -1'.
After cultivation and treatment, the results shown in Table 1 and 6 were obtained. Sensitizing Dye D-4 Example 9 A method of preparing an emulsion for the fifth layer will be described. A well-stirred gelatin solution (gelatin in 600% water)
30 g potassium bromide and 5 wt% thioether
HO(CH2) 25(CH2) 25(CH2) 2
Add 0H aqueous solution 30- and keep it at 75℃)
Solution I and Solution II described below were applied simultaneously for 20 minutes.
AgBrI core particles of 0.45p (iodine content
15 mol%). After that, add the following solution
and solution ■ for 30 minutes at the same time to determine the average particle size.
is 0.85p and the iodine content in the shell is 8 mol%.
Hedral monodisperse AgBr I particles were prepared and sodium thiosulfate
and chloroauric acid and 4-hydroxy-6-methyl-1°3.
Optimally chemically sensitized by adding 3a,7-chitrazaindene.
Ta. The yield of emulsion is 650 g. Solution ■ ■ [IV
AgNO3 (g) 20 - 80
-KBr (g) 1
2-58.4KI (g)
-3-6,4H20(mu) 320 22
0 480 350 How to make emulsion for the third layer
I will explain. Well-stirred gelatin aqueous solution (gelatin in 700 water
Contains 20g of chin and 3g of sodium chloride, kept at 75℃.
), sodium chloride and potassium bromide (total of 0.
800 d and o, 59 mol of an aqueous solution containing
Aqueous solution 600- containing acid silver and dye (a) solution at the same time
Addition was made at equal flow rates over 50 minutes. In this way,
Monodispersed dye adsorbed with an average particle size of 0.451L
A cubic silver chlorobromide emulsion (Br 80 mol %) was prepared. After washing with water and desalting, sodium thiosulfate and 4-biloxy-6
-Methyl-1,3,3a,7-chitrazaindene added
Optimal chemical sensitization was performed using The yield of emulsion is 600
It is g. Dye (A) Methanol 400mJL
The emulsion of Example 8 (■) was used as the emulsion for the first calendar, and the above emulsion and the emulsion were used as the emulsions for the third and fifth layers.
and the benzotriazole silver emulsion and dye-donor of Example 1
A photosensitive material with the composition shown in Table 7 was made using a dispersion of high quality.
Ta. Using the dye fixing material D-1 of Example 1, Example
The following results were obtained by performing the same operations and treatments as in 6. Color Image Highest density Lowest density Yellow
2.65 0.13 Magenta 2.30
0.12 cyan 2.30
0.14 The effects of the present invention are clearly demonstrated by the above examples.
It is clear.

Claims (1)

[Claims] At least a photosensitive silver halide on a support, a binder, and a dye-donating property that produces or releases a diffusible dye in response to or inversely to this reaction when the photosensitive silver halide is reduced to silver under high temperature conditions. A light-sensitive material containing a substance is heated in the presence of water and a base and/or a base precursor after or simultaneously with imagewise exposure, and the generated or released diffusible dye is converted into a dye during heating for development. An image forming method characterized by transferring to a fixed layer.