JPH0528820B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for forming a positive color image using an internal latent image type silver halide color photographic light-sensitive material for direct positive color image formation, and more specifically, the present invention relates to a method for forming a positive color image using an internal latent image type silver halide color photographic light-sensitive material for direct positive color image formation. The present invention relates to a new processing method that has less dependence on bromide ion concentration fluctuations and processing time dependence, does not impair rapidity, and has little development fog, and particularly relates to a processing method that requires a small amount of replenishment and has high processing stability. [Prior Art] Conventionally known methods for obtaining direct positive images are mainly divided into two types. One type uses a silver halide emulsion that has fog nuclei in advance, and uses solarization or the Herschel effect to destroy the fog nuclei or latent image in the exposed area, thereby producing a positive image after development. It is used to obtain images. The other type uses an internal latent image type silver halide emulsion that has not been fogged in advance, performs fogging treatment (development nucleation treatment) after image exposure, and then performs surface development, or performs fogging treatment after image exposure. A positive image can be obtained by performing surface development while performing (development nucleation treatment). The fogging treatment (development nucleation treatment) described above may be performed by exposing the entire surface to light, chemically using a fogging agent, or using a strong developer, and further heat treatment. etc. may also be used. Of the above two methods for forming a positive image, the latter type of method generally has higher sensitivity than the former type of method, and is suitable for applications requiring high sensitivity. Various techniques are known in this technical field. For example, US Pat. No. 2,592,250,
Same No. 2466957, No. 2497875, No. 2588982, Same No.
The methods described in No. 3761266, No. 3761276, No. 3796577, British Patent No. 1151363, etc. are known. In the case of processing internal latent image type silver halide color photographic light-sensitive materials (hereinafter referred to as internal latent image type light-sensitive materials), basically after fogging treatment and/or
Alternatively, it consists of two steps: color development and desilvering, which are carried out while performing a fogging treatment, and desilvering consists of a bleaching and fixing step or a bleach-fixing step. In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps. In color development performed after and/or while fogging, the silver halide in the unexposed area is reduced to silver, and at the same time, the oxidized aromatic primary amine developing agent is converted into a coupler. Reacts to form a pigment. In this process,
Halogen ions generated by reduction of silver halide are eluted and accumulated in the developer. Additionally, components such as inhibitors contained in the internal latent image type photosensitive material are also eluted into the color developing solution and accumulated. In the desilvering process, the silver produced by development is bleached with an oxidizing agent, and then all silver salts are converted into soluble silver salts with a fixing agent.
It is removed from the internal latent image type photosensitive material. A one-bath bleach-fixing method is also known in which the bleaching step and the fixing step are carried out simultaneously. In the color developing solution, as mentioned above, development inhibiting substances accumulate when the internal latent image type photosensitive material is developed, but on the other hand, the color developing agent and benzyl alcohol are consumed or accumulated in the internal latent image type photosensitive material. The concentration of these components decreases. Therefore, in a development method in which a large amount of internal latent image type photosensitive material is continuously processed using an automatic processor or the like, the components of the color developing solution are kept within a certain concentration range in order to avoid changes in development finish characteristics due to changes in component concentration. A means is needed to maintain it. As such a method, a method of replenishing a replenisher is usually used to supplement the missing components and dilute the unnecessary increased components. The replenishment of this replenisher inevitably results in large amounts of overflow, which are discarded, making this method a major economic and pollution problem.
Therefore, in recent years, in order to reduce the overflow liquid, a so-called concentrated low replenishment system has been proposed and put into practical use, in which the replenisher is concentrated and refilled in small amounts. [Problems to be Solved by the Invention] However, if the amount of replenishment is extremely reduced, the concentration of organic inhibitors and halogen ions eluted into the developer will change significantly even due to a slight error in the amount of replenishment. It also becomes susceptible to concentration due to evaporation, which usually results in an increase in the concentration of the fatigue deposits. For example, when the halogen ion concentration increases, the development reaction is suppressed, and in particular, the high-density portion of the characteristic curve is further suppressed, resulting in the problem that the density does not increase even if the processing time is extended, for example. In order to avoid this, for example, an overflow liquid is removed from the ion exchange resin as proposed in the processing of surface latent image type silver halide color photographic light-sensitive materials for normal negative image formation (hereinafter referred to as surface latent image type light-sensitive materials). One possible method is to remove halogen ions by electrodialysis, add a regenerating agent to compensate for the deficient components generated during development and the deficient components lost during regeneration processing, and regenerate and use it again as a replenisher. These regeneration and concentrated low replenishment methods using ion exchange resins and electrodialysis are susceptible to fluctuations in bromide ion concentration due to the effects of evaporation and regeneration operations, and are also affected by differences in throughput, evaporation, and replenishment volume. The disadvantage is that the composition of the processing solution varies widely due to For this reason, low-replenishment processing and recycling methods require efforts to quantitatively analyze the components and make the composition constant each time they are recycled. Therefore, it is difficult to implement these regeneration processing and low-replenishment processing in photo labs or mini-labs that do not have special skills. There are many things like that. These problems are mainly caused by changes in bromide ions, which are development inhibitors. For example, it is possible to improve developability by reducing the average particle size of silver halide in internal latent image type photosensitive materials. Although it is presumed that this problem can be solved, the conventional developing agent 3-methyl-4-amino-N-ethyl-N-β
- Contrary to the expectation that in color developing solutions using methanesulfonamidoethylaniline, improving developability would actually make them more susceptible to fluctuations in the bromide ion concentration in the developer, impairing processing stability. The result will be. However, it is an important issue to improve processing stability while shortening processing time. That is, the strong demand of the times is the above-mentioned low replenishment from an economical point of view, but there is also a strong demand for short processing times from the viewpoint of shortening delivery times. However, as described above, speeding up the process and stabilizing the process or reducing replenishment are contradictory issues and can be said to be a trade-off relationship. That is, if the replenishment level is low, the concentration of bromide ion, which is an inhibitor, and the concentration of ionic compounds and mercapto compounds, which are emulsion stabilizers, increase, impairing rapidity and processing stability. However, various measures have been taken to speed up color development. In particular, the above-mentioned developing agents, which have been conventionally used as the most suitable agents for developing internal latent image type silver chlorobromide emulsions, have low hydrophilicity, so that the color developing agents penetrate slowly into light-sensitive materials. Various penetrants have been studied to speed up color development, and for example, a method of speeding up color development by adding benzyl alcohol to a color developer is widely used. However, this method had the drawback that sufficient color development was not achieved unless the treatment was carried out at 33° C. for 3 minutes or more, and it was also sensitive to subtle bromide ion concentrations. Methods to raise the pH of the color developer are also known, but when the pH exceeds 10.5, the oxidation of the color developer becomes extremely rapid, and the lack of a suitable buffer makes it susceptible to changes in pH, resulting in stability. There were problems in that it became impossible to obtain the desired photographic characteristics, and the dependence on processing time increased. It is also known to increase the activity by increasing the color developing agent in the color developing solution, but the color developing agent is very expensive, resulting in a relatively expensive processing solution, and at the same time, the main agent is difficult to dissolve in water and tends to precipitate. It also causes instability and cannot be used practically. On the other hand, in order to speed up the color development of a surface latent image type photosensitive material, a method is known in which a color developing agent is incorporated in the photosensitive material in advance. For example, a method is known in which a color developing agent is converted into a metal salt and incorporated therein (US Pat. No. 3,719,492), but with this method, the raw storage stability of the photosensitive material is poor, the material is contaminated before use, and furthermore, during color development. It is known that it has the disadvantage of being easily fogged. Furthermore, in order to inactivate the amine moiety of the color developing agent, for example, there is a method of incorporating the color developing agent into a Schiff salt (US Pat. No. 3,342,559,
Research Disclosure, 1976 No. 15159) are also known, but these methods have the disadvantage that color development cannot begin until after the color developing agent has been alkaline hydrolyzed, and the color development is rather delayed. Are known. Furthermore, when the color developing agent is directly contained, the color developing agent is unstable, which causes the emulsion to fog during storage, and the emulsion film quality becomes weak, which causes various processing problems. It is known that there is. It has been found that the same drawbacks occur when techniques known for surface latent image type photosensitive materials as described above are applied to internal latent image type photosensitive materials. In addition, as accelerators conventionally known in surface latent image type photosensitive materials, U.S. Pat.
No. 2515147, No. 2496903, No. 4038075, No.
4119462, British Patent No. 1430998, British Patent No. 1455413,
JP-A No. 53-15831, No. 55-62450, No. 55-
As a result of examining the compounds described in Japanese Patent Publication No. 62451, No. 55-62452, No. 55-62453, Japanese Patent Publication No. 51-12322, Japanese Patent Publication No. 55-49728, etc., it was found that they do not have a promoting effect on internal latent image type photosensitive materials. Most of the compounds are sufficient;
Moreover, compounds exhibiting a high degree of accelerating effect not only have the disadvantage of producing fog during development, but are also unsuitable as a method for improving processing stability. Furthermore, in a surface latent image type photosensitive material, it is known that a silver halide emulsion layer which is substantially non-photosensitive is provided in the photosensitive material to accelerate development.
No. 56-14236, British Patent No. 1378577,
It is known from OLS2622922, etc., and its function is to adsorb development inhibiting substances such as unnecessary halogens released during development and unnecessary leaving groups of DIR couplers and DAR couplers, and actively promotes development. It's not something you do. In particular, even when applied to internal latent image type photosensitive materials, its development promotion effect is small, and although it is effective against fluctuations in iodide ion concentration, it has no processing stabilizing effect on fluctuations in bromide ion concentration. I couldn't get it. On the other hand, in the case of surface latent image type photosensitive materials, the speed of color development varies depending on the type of paraphenylenediamine derivative used and is said to depend on the redox potential. Among these color developing agents, N-alkyl-substituted color developing agents with low water solubility such as N,N-diethyl-p-phenylenediamine sulfate and 3-methyl-4-amino-N,N-diethylaniline hydrochloride are used. Although the main agent has high developing activity and can speed up development, it is known that the coloring dye after processing has a low dark brown color, which is undesirable, and even when applied to internal latent image type light-sensitive materials, the results are almost the same. , and stability against bromide ion concentration could not be obtained. On the other hand, surface latent image type photosensitive materials are said to have high development activity and are preferred (U.S. Pat. No. 3,656,950,
3-methyl-4-amino-
N-ethyl-N-β-methoxyethylaniline-
When di-p-toluene sulfonate was applied to an internal latent image type photosensitive material, although it did provide rapidity, stability against bromide ion concentration was not obtained and the internal latent image type photosensitive material remained untreated after processing. It was found that yellow stains were significantly generated in the exposed areas, and especially when processed for a short time, the color developing agent remained and caused rough stains, making it impossible to use in rapid processing. On the other hand, 3-methyl-4-amino-N-ethyl-β, which has a water-soluble alkylsulfonamide group or hydroxyalkyl group introduced into the N-alkyl group,
- Methanesulfonamidoethylaniline sesquisulfate monohydrade, 3-methyl-4-amino-N-β-hydroxyethylaniline sulfate, etc.
Engineering Vol.8, No.5-June, 1964,
As seen on pages 125 to 137, there was not much difference in the half-wave potential indicating the oxidation-reduction potential, and both were said to have weak developing activity. Therefore, it is said that there are almost no color developing agents that have high development activity and excellent processing stability for internal latent image type silver chlorobromide emulsions, and 3-methyl-4
-Amino-N-ethyl-N-β-methanesulfonamidoethylaniline sulfate was used with benzyl alcohol. However, in this case, as described above, it is susceptible to changes in bromide ion concentration. In addition, in the concentrated low replenishment process that reduces the amount of replenisher,
There is a problem in that the rate at which the tank liquid is renewed with the replenisher becomes low and the period of use of the liquid becomes long, resulting in decomposition of the active ingredients and a decrease in the activity of the liquid. Another problem is an increase in the contamination and accumulation of other processing liquid components, and when this is combined with the extension of the liquid usage period associated with the above-mentioned concentrated and low replenishment processing, the contamination and accumulation of other processing liquid components is increasing. The impact will be greater.
Contamination with other processing solutions is caused by so-called back contamination, in which processing solution components immediately after development are brought into the color developer by splashes of neighboring processing solutions in the processing machine, transport leaders, belts, hangers for hanging the film, etc. caused. Among these accumulated mixed components, thiosulfate ion, which is a fixing agent, dissolves silver halide and promotes physical development. As a result, exposed areas with latent images inside are developed, resulting in significant development fog. That is, this problem occurs particularly when bleach-fixing is performed directly after color development. Further, increased contamination of metal salts as bleaching agents, especially ferric salts, accelerates the decomposition of hydroxylamine as a preservative, producing ammonia ions. This decomposition reaction is greatly accelerated at temperatures above 30°C. The generation of ammonia ions accelerates physical development in the same way as thiosulfate ions, and has the disadvantage of causing development fog. Therefore, even if the amount of replenishment is reduced for economical reasons and to improve environmental pollution, rapid processing is possible, photographic performance is maintained constant, and the active ingredients do not decompose even if the processing solution is used for a long time. At present, there is a strong desire for a color developing solution that can be stably processed without causing any change in photographic processing performance. The first object of the present invention is to maintain constant appropriate photographic performance over a long period of time without any change in bromide ion concentration even when processed with a color developing solution at a low replenishment amount, and to eliminate development fog. An object of the present invention is to provide a method for forming a direct positive color image quickly and stably without generation. As a result of various studies to achieve the first object of the present invention, the present inventors have discovered a unique color developing agent that is almost unaffected by the bromide ion concentration when developing a specific silver halide, and has further developed such a color developing agent. Although we succeeded in finding a method to effectively suppress the development fog that occurs when using a developing agent, we encountered the following obstacles. In other words, if the processing amount is small, the renewal rate of the color developer in the processing tank by the replenisher will be significantly reduced, and the stagnation time of the color developer will become longer, resulting in a decrease in the concentration of cyan dye. It has been found that there is a close relationship between the decrease in the activity of the color developing solution due to the extension of the retention time and the shortening of the development processing time due to the increase in speed. That is, a second object of the present invention is to provide a method for forming a direct positive color image that can prevent cyan dye from deteriorating even if the throughput is reduced and the stagnation time of the color developer is prolonged. [Means for Solving the Problems] The present invention, which achieves the first and second objects described above, provides at least one photosensitive layer containing internal latent image type silver halide grains whose grain surfaces are not fogged in advance. In a method of directly forming a positive color image by subjecting an internal latent image type photosensitive material having a photosensitive emulsion layer to imagewise exposure and then color development, the silver halide emulsion in at least one photosensitive emulsion layer is substantially chlorobrominated. It is a silver emulsion, and the average grain size of silver halide grains in at least the blue-sensitive emulsion layer is 1.4 μm or less, and the red-sensitive emulsion layer has the following general formula [], [] or []
An internal latent image type photosensitive material containing at least one type of cyan coupler represented by (hereinafter referred to as the cyan coupler of the present invention) is prepared by adding an N-hydroxyalkyl-substituted p-phenylenediamine derivative and at least 5× It is characterized by developing at a temperature of 30°C or more and 150 seconds or less using a color developing solution containing 10 ^-3 mol/bromide. General formula [] In the formula, one of R and R ₁ is a hydrogen atom, the other is a linear or branched alkyl group having at least 2 to 12 carbon atoms, and X is a hydrogen atom or N-hydroxyalkyl-substituted-p-phenylenediamine It represents a group that can be separated by a coupling reaction with an oxidized form of a derivative color developing agent, and R ₂ represents a ballast group. General formula [] General formula [] In the formula, Y is −COR ₄ ,

[Formula] −SO ₂ R ₄ ,

【formula】

[Formula] -CONHCOR ₄ or -CONHSO ₂ R ₄ (However, R ₄ represents an alkyl group, alkenyl group, cycloalkyl group, aryl group, or heterocyclic group, and R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group,
It represents a cycloalkyl group, an aryl group, or a heterocyclic group, and R ₄ and R ₅ may be combined with each other to form a 5- to 6-membered heterocycle. ), R ₃ represents a ballast group, and Z represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an N-hydroxyalkyl-substituted p-phenylenediamine derivative color developing agent. The present inventor has developed a method for color development when developing an internal latent image type light-sensitive material using an internal latent image type emulsion containing a specific silver halide, that is, silver chlorobromide (in particular, the silver bromide content is 90 mol% or less). We have found the surprising fact that only when an N-hydroxyalkyl-substituted p-phenylenediamine derivative is used as the main ingredient, the dye density obtained hardly decreases even if the bromide ion concentration increases. The above-mentioned characteristics of this color developing agent cannot be obtained with internal latent image type light-sensitive materials using substantially silver iodobromide emulsions containing 0.5 mol% or more of silver iodide. This is unexpected because it has been used exclusively for developing surface latent image type photosensitive materials using silver iodobromide emulsions, and it is also understandable from the redox potential and half-wave potential of common color developing agents. This is not something that can be done, but is unlikely to occur unless an optimal balance between development speed and coupling speed is maintained and fogging nuclei on the surface of unexposed silver halide grains formed by fogging treatment are efficiently developed. , which was surprising. However, the inventor encountered the following problem. It is rapid and insensitive to changes in bromide ion concentration when using N-hydroxyalkyl-substituted-p-phenylenediamine color developing agents;
In particular, since development can be performed under high bromide ion concentrations, the amount of replenishment can be greatly reduced during continuous processing, and processing stability is extremely high, which is a major advantage, but it has the disadvantage that development fog is likely to occur. I found out. The inventors of the present invention have made further efforts to solve this problem and have found that the problem can be solved by particularly performing the color development process in a short period of time.
However, shortening the color development time cannot be achieved unless the development processability of the color photographic light-sensitive material is sufficiently improved, and although it cannot be shortened unconditionally, it is possible to achieve low replenishment and processing stability without developing fog. It has been found that in order to achieve this, processing must be performed at 30°C or higher and within 150 seconds using the color developing solution of the present invention. In this case, if conventional internal latent image type photosensitive materials are used as they are, there will be a problem that developing time will be insufficient and sufficient photographic images will not be obtained. Therefore, the inventors of the present invention have made further studies, and in order to carry out low replenishment processing without being affected by the increase in bromide ion concentration using the color developing agent of the present invention, the present inventors have developed a method for forming at least one layer, preferably all of the photosensitive emulsion layers. An internal latent image type in which the silver halide emulsion is substantially a silver chlorobromide emulsion, and the average grain size of the silver halide grains in at least the blue-sensitive emulsion layer (preferably all light-sensitive emulsion layers) is 1.4 μm or less. By treating the photosensitive material with a developer containing an N-hydroxyalkyl-substituted p-phenylenediamine derivative, the development speed is improved, and this color photographic material can rapidly develop color within a range of 30°C or higher and 150 seconds or less. By developing the film, it was possible to achieve the first object of the present invention without developing fog. However, as a result of further studies, the inventor of the present invention found that in concentrated low replenishment processing, the rate at which the tank liquid is renewed with replenisher is low, and the period of use of the liquid becomes longer; It has been found that as the developer stagnates for a long time, the active ingredients decompose and the activity decreases, resulting in a decrease in the concentration of cyan dye in particular. It has also been found that this problem is particularly likely to occur when the development processing time is 150 seconds or less. The inventors of the present invention have conducted further studies and found that this problem can be effectively solved by using the cyan coupler of the present invention. This effect can only be obtained by using the color developing agent of the present invention, and is due to efficient development of surface fogging nuclei of unexposed silver halide grains formed by fogging treatment and development. This effect was obtained only by the combination of the thus-formed quinone diimine and the coupler with an efficient coupling reaction, and was a completely unexpected effect. As used herein, "substantially silver chlorobromide emulsion"
means that it may contain a trace amount of silver iodide in addition to silver chlorobromide, for example, it may contain 0.3 mol% or less, more preferably 0.1 mol% or less of silver iodide. . However, silver chlorobromide emulsions containing no silver iodide are most preferred in the present invention. The present invention will be explained in more detail below. The internal latent image type photosensitive material processed according to the present invention has at least one photosensitive emulsion layer containing internal latent image type silver halide grains whose grain surfaces are not fogged in advance. The meaning that the particle surface is not fogged in advance means that a test piece coated with the emulsion used in the present invention at a concentration of 35 mgAg/cm ² on a transparent film support was coated with the following surface developer A without exposure. The density obtained when developing for 10 minutes at 20°C is 0.6, preferably 0.4.
It means not to exceed. Surface developer A Metol 2.5g - Ascorbic acid 10g NaBO _{2.4H 2} O 35g KBr 1g Add water 1 In addition, the silver halide emulsion according to the present invention can be prepared by exposing the test piece prepared as described above to light. It provides sufficient density when developed with internal developer B having the following formulation. Internal developer B Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Sodium carbonate (-hydrate) 52.5g KBr 5g KI 0.5g Add water 1 To be more specific, a portion of the above test piece was When exposed to a light intensity scale for a defined time up to 2 seconds and developed in internal developer B for 10 minutes at 20°C, another part of the specimen exposed under the same conditions was exposed to surface developer B. A maximum density of at least 5 times, preferably at least 10 times, that obtained when developed for 10 minutes at 20°C. It is sufficient that at least one of the light-sensitive emulsion layers of the internal latent image type light-sensitive material processed according to the present invention consists essentially of a silver chlorobromide emulsion; Preferably, the emulsion is composed of a silver oxide emulsion.
The smaller the mole % of silver bromide in the silver chlorobromide, the more sufficient dye formation can be obtained even during color development in a short time.
Silver bromide content is preferably 90 mol% or less, preferably 70 mol%
The most preferable result is 40 mol% or more. In this specification, the average particle size r- means the particle size ri at which the product ni x ri ³ of the frequency ni of particles having the particle size ri and ri ³ is the maximum (3 significant figures, the smallest digit is 4 ). In the case of spherical silver halide grains, the grain size here means the diameter thereof, or in the case of grains having a shape other than spherical, the diameter when its projected image is converted into a circular image of the same area. The particle size can be obtained, for example, by magnifying the particles 10,000 to 50,000 times with an electron microscope and projecting the particles, and actually measuring the particle diameter or the area at the time of projection on the print (the number of particles measured is nil). Suppose there are more than 1000 discrimination items). In this specification, the term average particle size shall be used in the meaning defined above. The average grain size of the blue-sensitive emulsion layer (preferably all light-sensitive emulsion layers) of the present invention is preferably 1.4 μm or less, and the maximum effect can be obtained especially when it is 1.0 μm or less. Color development processing is performed at 30℃ or higher.
The processing time is 150 seconds or less, preferably 33° C. or higher and 120 seconds or less, most preferably 35° C. or higher and 90 seconds or less. If the processing is performed at 30° C. or higher and 150 seconds or longer, development fog worsens. In particular, processing time is more important than temperature, and if it exceeds 150 seconds, the development fog of the top layer will increase significantly, which is undesirable. In the present invention, the processing time of color development processing refers to the time from the start of fogging processing until the start of the next processing (for example, bleach-fixing processing), and the pre-soaking time before photofogging processing is the processing time. It is not included in. The processing temperature is raised to complete the development in a short time, but if it is too high, the development fog will increase, so it is preferably 30°C or higher and 50°C or lower, and particularly preferably 33°C or higher and 48°C or higher. ℃
The temperature is most preferably 35°C or higher and 43°C or lower. The developing agent effective in the present invention is a quaternary ammonium salt of an N-hydroxyalkyl-substituted p-phenylenediamine compound, particularly a compound represented by the following general formula (X).
It can be expressed as General formula (X) In the formula, R _{10 1} is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and R _{10 2} is a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms. It is an alkyl group having a carbon atom, and R _{10 3} is 1 to 4 which may have a hydroxyl group.
A is an alkyl group having at least one hydroxyl group and may have a branch, more preferably It is. R _{10 4} , R _{10 5} , and R _{10 6} each represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms that may have a hydroxyl group, and R _{10 4} ,
At least one of R _{10 5} and R _{10 6} is a hydroxyl group or an alkyl group having a hydroxyl group. n ₁ , n ₂ , n ₃ are each 0, 1, 2 or 3, and HX represents hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, nitric acid or phosphoric acid. Such p-phenylenediamine color developing agents are unstable in their free amines and are commonly used as salts (most commonly as specified by the above formula). A typical example is 4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline salt and 4-amino-N-ethyl-N-(β-hydroxyethyl)-
Examples include aniline salts. Preferably, in the present invention 4-amino-3
-Methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate-hydrate [this is CD-4
It is commercially available under the name
C41 system and Konishiroku Photo Industries Co., Ltd.'s CNK-4 system) used for developing color negative films] was found to be particularly effective. Preferred N-hydroxyalkyl-substituted p-phenylenediamine derivatives used in the present invention include the following, but are not limited to these exemplified compounds. Hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid salts of the compounds (1) to (8) above are particularly preferred. Among these exemplified compounds, Nos. (1), (2), (6), (7) and (8) are preferably used, and Nos. (1), (2) and (6) are particularly preferably used. Furthermore, especially No.(1)
However, it is preferably used in the present invention. Since the color developing agent of the present invention has extremely high solubility in water, the amount used is 1 g or more per processing solution.
It is preferably used in a range of 100g, more preferably in a range of 3g to 30g. These N-hydroxyalkyl-substituted -
p-phenylenediamine derivatives are published in the Journal of American Chemical Society 73.
It can be easily synthesized by the method described in Vol., p. 3100 (1951). The cyan coupler according to the present invention can be represented by the above general formulas [] to [], and the general formula [] will be further explained. In the present invention, R ₁ and R ₂ of the general formula []
The linear or branched alkyl group having 2 to 12 carbon atoms represented by is, for example, an ethyl group, a propyl group, or a butyl group. In the general formula [], the ballast group represented by R ₂ is of a size and shape that provides the coupler with sufficient bulk to make it substantially unable to disperse into other layers from the layer to which it is applied. It is an organic group having Typical ballast groups include alkyl groups or aryl groups having 8 to 32 carbon atoms in total, preferably ballast groups having 13 to 32 carbon atoms in total.
It is 28. These alkyl groups and aryl groups may have a substituent, and examples of the substituent for this aryl group include an alkyl group, an aryl group, an alkoxy group, an allyloxy group, a carboxy group, an acyl group, an ester group, and a hydroxy group. , a cyano group, a nitro group, a carbamoyl group, a carbonamide group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfonamide group, a sulfamoyl group, and a halogen. Examples of substituents for the alkyl group include the above-mentioned aryl groups except for the alkyl group. Examples include the substituents listed above. Preferred ballast groups are those represented by the following general formula. R ₁₂ represents an alkyl group having 1 to 12 carbon atoms, and Ar represents an aryl group such as a phenyl group, and this aryl group may have a substituent. Substituents include alkyl groups, hydroxy groups, halogen atoms,
Examples include alkylsulfonamide groups, and the most preferred are branched alkyl groups such as t-butyl. As is well known to those skilled in the art, the group defined by Affects gender. Typical examples include halogens such as chlorine and fluorine, aryloxy groups, substituted or unsubstituted alkoxy groups, acyloxy groups, sulfonamide groups, arylthio groups, heteroylthio groups, heteroyloxy groups, sulfonyloxy groups,
Examples include carbamoyloxy group. More specific examples include JP-A-50-10135 and JP-A-50-10135;
No. 120334, No. 50-130414, No. 54-48237, No.
No. 51-146828, No. 54-14736, No. 47-37425,
No. 50-123341, No. 58-95345, Special Publication No. 1977-
36894, U.S. Patent No. 3476563, U.S. Patent No. 3737316, U.S. Pat.
Examples include groups described in No. 3227551 and the like. Examples of cyan coupler compounds represented by the general formula [] will be listed below, but the invention is not limited thereto. Examples of the exemplified compounds include those in the general formula [] in which R ₁ , X, R ₂ and R are specified as shown below.

【table】

【table】

【table】

【table】

[Table] The synthesis method of the exemplified compounds of the present invention is shown below, but other exemplified compounds can also be synthesized by the same method. Synthesis example of exemplified compound C-5 [(1)-a] 2-nitro-4,6-dichloro-
Synthesis of 5-ethylphenol 33g of 2-nitro-5-ethylphenol, iodine
0.6 g and 1.5 g of ferric chloride are dissolved in 150 ml of glacial acetic acid. Add 3 ml of sulfuryl chloride to this at 40℃.
Drip in time. The precipitate formed during the dropwise addition is reacted and dissolved by heating and refluxing after the completion of the dropwise addition of sulfuryl chloride. Heating to reflux takes about 2 hours. The reaction solution is poured into water and the crystals produced are purified by recrystallization with methanol. (1)-a was confirmed by nuclear magnetic resonance spectroscopy and elemental analysis. [(1)-b] 2-nitro-4,6-dichloro-
Synthesis of 5-ethylphenol 21.2 g of the compound [(1)-a] was dissolved in 300 ml of alcohol, a catalytic amount of Raney nickel was added thereto, and hydrogen was passed through the solution at normal pressure until no hydrogen was absorbed. After the reaction, Raney nickel was removed and alcohol was distilled off under reduced pressure. The residue [(1)-b] was subjected to the next acylation without being purified. [(1)-c] Synthesis of 2[2,4-di-tert-acylphenoxy)acetamide]-4,6-dichloro-5-ethylphenol 18.5 g of crude amide obtained in [(1)-b] of
It is dissolved in a mixture of 500 ml of glacial acetic acid and 16.7 g of sodium acetate, and an acetic acid solution prepared by dissolving 28.0 g of 2,4-di-tert-acylphenoxyacetic acid chloride in 50 ml of acetic acid is added dropwise thereto at room temperature. Drip in 30 minutes,
After stirring for an additional 30 minutes, the reaction solution was poured into ice water.
The generated precipitate is collected by filtration, dried, and then recrystallized twice from acetonitrile to obtain the desired product. The target product was confirmed by elemental analysis and nuclear magnetic resonance spectroscopy.

[Table] Next, the cyan coupler represented by the general formula [] or [] used in the present invention will be explained. In the general formulas [] and [], Y
is −COR ₄ ,

[Formula] −SO ₂ R ₄ ,

【formula】

[Formula] A group represented by -CONHCOR ₄ or -CONHSO ₂ R ₄ . However, R ₄
is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (allyl group, heptadecenyl group, etc.) ), cycloalkyl group, preferably 5-7
membered rings (e.g., cyclohexyl, etc.), aryl groups (e.g., phenyl, tolyl, naphthyl, etc.), heterocyclic groups, preferably 5- to 6-membered groups containing 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms. Ring heterocyclic groups (e.g. furyl group, thienyl group,
benzothiazolyl group, etc.). R ₅ represents a hydrogen atom or a group represented by R ₄ . R ₄ and R ₅ may be combined with each other to form a 5- to 6-membered heterocycle. Note that any substituent can be introduced into R ₂ and R ₃ , such as an alkyl group having 1 to 10 carbon atoms (for example, methyl, i-propyl, i-butyl, t-
-butyl, t-octyl, etc.), aryl groups (e.g. phenyl, naphthyl, etc.), halogen atoms (fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide groups (e.g. methanesulfonamide, butanesulfonamide, p- toluenesulfonamide, etc.), sulfamoyl groups (e.g., methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl groups (e.g., methanesulfonyl, p-toluenesulfonyl, etc.), fluorosulfonyl groups, carbamoyl groups (e.g., dimethylcarbamoyl, phenylsulfonyl, etc.), carbamoyl, etc.), oxycarbonyl groups (e.g., ethoxycarbonyl, phenoxycarbonyl, etc.),
Acyl groups (e.g. acetyl, benzoyl, etc.), heterocyclic groups (e.g. pyridyl, pyrazolyl, etc.),
Examples include an alkoxy group, an aryloxy group, an acyloxy group, and the like. In general formula [] and general formula [], R ₃
represents a ballast group necessary for imparting diffusion resistance to the cyan coupler represented by the general formula [] and the general formula [] and the cyan dye formed from the cyan coupler. Preferred are alkyl groups, aryl groups, and heterocyclic groups having 4 to 30 carbon atoms. Examples include linear or branched alkyl groups (eg, t-butyl, n-octyl, t-octyl, n-dodecyl, etc.), alkenyl groups, cycloalkyl groups, 5- or 6-membered heterocyclic groups, and the like. In general formula [] and general formula [], Z is a hydrogen atom or N-hydroxyalkyl substituted -p-
Represents a group that can be separated during a coupling reaction with an oxidized form of a phenylenediamine derivative developing agent. For example, halogen atoms (e.g. chlorine, bromine, fluorine, etc.), substituted or unsubstituted alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups,
Examples include a carbamoyloxy group, a sulfonyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfonamide group, and more specific examples include U.S. Pat.
No. 37425, Japanese Patent Publication No. 1973-36894, Japanese Patent Publication No. 1973-10135
No. 50-117422, No. 50-130441, No. 51-
No. 108841, No. 50-120343, No. 52-18315, No.
No. 53-105226, No. 54-14736, No. 54-48237,
No. 55-32071, No. 55-65957, No. 56-1938,
No. 56-12643, No. 56-27147, No. 59-146050
No. 59-166956, No. 60-24547, No. 60-
Examples include those described in No. 35731 and No. 60-37557. In the present invention, among the cyan couplers represented by the general formula [] or [], cyan couplers represented by the following general formula [], [] or [] are more preferred. General formula [] General formula [] General formula [] In the general formula (), R ₁₃ is a substituted or unsubstituted aryl group (particularly preferably a phenyl group). When the aryl group has a substituent, examples of the substituent include SO ₂ R ₁₆ , a halogen atom ( Basic,
(chlorine, bromine, etc.), -CF ₃ , -NO ₂ , -NO ₂ , -CN, -
COR ₁₆ , −COOR ₁₆ , −SO ₂ OR ₁₆ ,

【formula】

[Formula] −OR ₁₆ , − OCOR ₁₆ ,

【formula】

[Formula] and

At least one substituent selected from the formula is included. Here, R ₁₆ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl,
tert-butyl, dodecyl groups, etc.), alkenyl groups, preferably alkenyl groups having 2 to 20 carbon atoms (allyl groups, heptadecenyl groups, etc.), cycloalkyl groups, preferably 5- to 7-membered ring groups (for example, cyclohexyl, etc.) , represents an aryl group (eg, phenyl group, tolyl group, naphthyl group, etc.), and R ₁₇ is a hydrogen atom or a group represented by R ₁₆ . In a preferred compound of the cyan coupler of the present invention represented by the general formula [], R ₁₃ is a substituted or unsubstituted phenyl group, and the substituent to the phenyl group is cyano, nitro, -SO ₂ R ₁₈ (R ₁₈ is an alkyl group),
This is a compound that is a halogen atom or trifluoromethyl. In general formulas [] and [], R ₁₄ , R ₁₅
is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, tert-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (allyl group, oleyl group) etc.), cycloalkyl groups, preferably 5- to 7-membered ring groups (e.g. cyclohexyl, etc.), aryl groups (e.g. phenyl, tolyl, naphthyl, etc.),
Heterocyclic group (for example, a 5- to 6-membered heterocyclic ring containing 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms is preferable, such as furyl group, thienyl group,
Examples include benzothiazolyl group. ) represents. The above R ₁₆ , R ₁₇ and general formulas [] and []
Any substituent can be further introduced into R ₁₄ and R ₁₅ , specifically, a substituent such as the one that can be introduced into R ₄ or R ₅ in the general formulas [] and []. . As a substituent, a halogen atom (chlorine atom, fluorine atom, etc.) is particularly preferable. In the general formulas [], [] and [], Z and
R ₃ has the same meaning as in the general formulas [] and [], respectively. A preferred example of the ballast group represented by R ₃ is a group represented by the following general formula []. General formula [] In the formula, J represents an oxygen atom, a sulfur atom or a sulfonyl group, K represents an integer of 0 to 4, represents 0 or 1, and when K is 2 or more, two or more are present.
R ₂₀ may be the same or different. R ₁₉ represents a linear or branched alkylene group having 1 to 20 carbon atoms, and a substituted alkylene group such as an aryl group, and R ₂₀ represents a monovalent group, preferably a hydrogen atom, a halogen atom (e.g. chromium, bromine), Alkyl groups, preferably linear or branched alkyl groups having 1 to 20 carbon atoms (e.g., methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.), aryl groups ( (e.g., phenyl group), heterocyclic group (e.g., nitrogen-containing heterocyclic group), alkoxy group, preferably linear or branched carbon number 1-
20 alkoxy groups (e.g. methoxy, ethoxy,
t-butyloxy, octyloxy, decyloxy, dodecyloxy, etc.), aryloxy groups (e.g. phenoxy), hydroxy groups, acyloxy groups, preferably alkylcarbonyloxy groups, arylcarbonyloxy groups (e.g. acetoxy, benzoyloxy) groups (e.g. acetoxy group, benzoyloxy group), carboxy,
an alkyloxycarbonyl group, preferably a straight or branched alkylcarbonyl group having 1 to 20 carbon atoms,
Preferably a phenoxycarbonyl group, an alkylthio group, preferably an acyl group having 1 to 20 carbon atoms, preferably a linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, an acylamino group, preferably a C1 to 20 group. Straight chain or branched alkylcarboxamide group, benzenecarboxamide group, sulfonamide group, preferably straight chain or branched alkylsulfonamide group or benzenesulfonamide group having 1 to 20 carbon atoms, albamoyl group, preferably carbon number 1 ~
It represents a straight chain or branched alkylaminocarbonyl group having 20 carbon atoms or a phenylaminocarbonyl group, a sulfamoyl group, preferably a straight chain or branched alkylaminosulfonyl group having 1 to 20 carbon atoms, a phenylaminosulfonyl group, or the like. Next, specific examples of compounds of the cyan coupler represented by the general formula [] or [] will be shown, but the invention is not limited thereto. These cyan couplers of the present invention can be synthesized by known methods, and in the case of compounds represented by the general formula [], for example, US Pat.
It can be synthesized by the synthesis method described in 3446622, 3996253, British Patent No. 1011940, etc. In addition, in the case of a compound represented by the general formula [],
For example, US Patent No. 2772162, US Patent No. 3758308, US Patent No.
No. 3880661, No. 4124396, British Patent No. 975773,
No. 8011693, No. 8011694, JP-A-47-21139,
No. 50-112038, No. 55-163537, No. 56-29235
No. 55-99341, No. 56-116030, No. 52-
No. 69329, No. 56-55945, No. 56-80045, No. 50
−134644 and UK Patent No. 1011940, US Patent
No. 3446622, No. 3996253, JP-A-56-65134,
No. 57-204543, No. 57-204544, No. 57-204545
No., Patent Application No. 56-131309, No. 56-131311, No. 56
−131312, No. 56-131313, No. 56-131314,
No. 56-130459, No. 57-149791, JP-A-59-
No. 146050, No. 59-166956, No. 60-24547, No. 146050, No. 59-166956, No. 60-24547, No.
It can be synthesized by the synthesis method described in No. 60-35731, No. 60-37557, etc. The cyan coupler represented by the general formula [], [] or [] can be used in combination with a cyan coupler other than the present invention to the extent that it does not contradict the purpose of the present invention. Furthermore, one or more cyan couplers of the general formulas [], [] and [] can be used in combination. When the cyan coupler according to the present invention represented by the general formulas [] to [] is contained in the silver halide emulsion layer, it is usually about
It is used in a range of 0.005 to 2 mol, preferably 0.01 to 1 mol. The internal latent image type photosensitive material of the present invention can be image-exposed (photographed) in a conventional manner and then subjected to surface development to easily obtain a positive image directly. That is, the main step of directly creating a positive image is to subject the internal latent image type photosensitive material of the present invention to a process of generating fog nuclei by chemical action or photochemical action after image exposure, that is, a fog process. after and/
Alternatively, surface development may be performed while performing fogging treatment. Here, the fogging treatment can be carried out using a compound that provides full exposure or generates fogging nuclei, that is, a fogging agent. In the present invention, it is preferable that the fogging treatment be carried out by exposing the entire surface to light since the dye concentration will not decrease as the bromide ion concentration increases. In addition, since full-surface exposure is usually applied within or outside the developer after the image-exposed photosensitive material is immersed in the developer, the renewal rate of the developer decreases due to low replenishment processing.
Although the developer is easily affected by coloring and tarring caused by a long retention time of the developer, the color developing agent of the present invention has less such coloring and tarring, and is particularly effective for fogging treatment when full exposure is applied. Suitable for low replenishment processing carried out by In the present invention, the entire surface exposure is carried out by immersing or moistening the image-exposed internal latent image type photosensitive material in a developer or other aqueous solution, and then uniformly exposing the entire surface. The light source used here may be any light within the sensitive wavelength range of the internal latent image type photosensitive material, and high-intensity light such as flash light can be applied for a short time, or weak light can be applied for a long time. It's okay. The illuminance of such light fogging can be adjusted by changing the luminous intensity of the light source, by reducing the light using various filters, by using the distance between the photosensitive surface and the light source, and by using the angle between the photosensitive surface and the light source. can. Furthermore, in order to shorten the exposure time for light fogging, it is also possible to adopt a method of fogging with weak light at the initial stage of exposure and then fogging with stronger light. Further, the total exposure time can be varied over a wide range depending on the internal latent image type photosensitive material, development processing conditions, type of light source used, etc. so as to ultimately obtain the best positive image. Full exposure is also possible using a light source installed outside the developer.
It may be applied to the internal latent image type photosensitive material in the developer solution, or it may be applied to the internal latent image type photosensitive material once taken out of the developer solution. Further, a light source provided in the developer may be used to expose the entire surface to light during development, or a combination of these may be used. In the present invention, the fogging process may be carried out by developing in the presence of a fogging agent, but in this case, a wide variety of compounds can be used as the fogging agent, and this fogging agent is used during the developing process. For example, it may be contained in a constituent layer other than the support of a photographic light-sensitive material (among them, a silver halide emulsion layer is particularly preferred), or in a developer or a processing solution prior to development.
The amount used can vary widely depending on the purpose, and the preferred amount is 1 to 1,500 mg, preferably 10 to 1,000 mg per mole of silver halide when added to a silver halide emulsion layer. .
In addition, when added to a processing solution such as a developer, the preferable amount of addition is 0.01 to 5 g/, particularly preferably 0.05 to 5 g/
1g/. Examples of the fogging agent used in the present invention include hydrazines described in U.S. Pat. No. 2,563,785 and U.S. Pat. No. 3719494, same
Heterocyclic quaternary nitrogen salt compounds described in US Pat. No. 3,734,738 and US Pat.
Examples include compounds having adsorption groups on the silver halide surface. Moreover, these fogging agents can also be used in combination. For example, Research Disclosure No. 15162 describes the use of a non-adsorption type fogging agent in combination with an adsorption type fogging agent, and this combination technique is also effective in the present invention. As the fogging agent used in the present invention, either an adsorption type or a non-adsorption type can be used, and they can also be used in combination. Specific examples of useful fogging agents include hydrazine hydrochloride, phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2-
(4-methylphenyl)hydrazine, 1-acetyl-2-phenylhydrazine, 1-acetyl-2
-(4-acetamidophenyl)hydrazine, 1
-methylsulfonyl-2-phenylhydrazine, 1-benzoyl-2-phenylhydrazine,
Hydrazine compounds such as 1-methylsulfonyl-2-(3-phenylsulfonamidophenyl)hydrazine and formaldehyde phenylhydrazine; 3-(2-formylethyl)-2-methylbenzothiazolium bromide , 3-(2-formylethyl)-2-propylbenzothiazolium bromide, 3-(2-acetylethyl)-2-benzylbenzoselenazolium bromide, 3-(2
-acetylethyl)-2-benzyl-5-phenyl-benzoxazolium bromide, 2-methyl-3-[3-(phenylhydrazino)propyl]
Benzothiazolium bromide, 2-methyl-3
-[3-(p-tolylhydrazino)propyl]benzothiazolium bromide, 2-methyl-3-
[3-(p-sulfofenylhydrazino)propyl]benzothiazolium bromide, 2-methyl-3-[3-(p-sulfofenylhydrazino)
pentyl] benzothiazolium iodide, 1,2
-dihydro-3-methyl-4-phenylpyrido[2,1-b]benzothiazolium bromide,
1,2-dihydro-3-methyl-4-phenylpyrido[2,1-b]-5-phenylbenzoxazolium bromide, 4,4'-ethylenebis(1,2-dihydro-3-methylpyrido[2 ,1
-b] benzothiazolium bromide), 1,2
-N-substituted quaternary cycloammonium salt such as dihydro-3-methyl-4-phenylpyrido[2,1-b]benzoselenazolium bromide; 5-
[1-Ethylnaphtho(1,2-b)thiazoline-
2-ylideneethylidene]-1-(2-phenylcarbazoyl)methyl-3-(4-sulfamoylphenyl)-2-thiohydantoin, 5-(3-ethyl-2-benzothiazolinylidene) )-3-[4-
(2-formylhydrazino)phenyl]rhodanine, 1-[4-(2-formylhydrazino)phenyl]3-phenylthiourea, 1,3-bis[4-(2-formylhydrazino)phenyl ) phenyl]thiourea and the like. The color developing solution of the present invention has a bromide ion concentration of 5×
The bromide ion concentration is preferably 10 ^-3 mol or more, but in the present invention, the higher the bromide ion concentration, the lower the replenishment amount, so it is preferable.
In conventional development methods, it has been said that the lower the bromide ion concentration is, the better because it suppresses the development reaction, but in the combination of the internal latent image type photosensitive material and developer of the present invention, the higher the bromide ion concentration is, the more preferable it is. The objectives of the invention are achieved. In other words, in the present invention, the amount of replenishment can be reduced because it is less affected by the bromide ion concentration. The bromide ion concentration is preferably 1 x 10 ^-2 mol or more, particularly preferably 1.5 x 10 ^-2 mol or more,
If the bromide ion concentration is too high, development will be inhibited and the bromide ion concentration will begin to have an effect.
10 ⁻² mol or more is not preferable. Note that the concentration of chloride has no effect. In the processing method of the internal latent image type photosensitive material of the present invention, it is possible to use a color developing bath containing the color developing agent according to the present invention. In addition, various other methods such as bath processing, such as a spray method in which a processing liquid is atomized, a wet method in which contact is made with a carrier impregnated with a processing liquid, and a developing method using a viscous processing liquid, are also available. method can be used. In addition to the above, there are no particular limitations on the processing method for the internal latent image type photosensitive material of the present invention, and any processing method can be applied. For example, representative methods include a method of performing bleach-fixing treatment after color development and further washing with water and/or stabilization treatment if necessary;
After color development, bleaching and fixing are performed separately, and if necessary, further water washing and/or stabilization treatment is performed; or pre-hardening, neutralization, color development, stop fixing, water washing, bleaching, fixing, water washing, and post-hardening. A method in which the process is performed in the order of hardening and water washing; a method in which the process is performed in the order of color development, water washing, supplementary color development, stopping, bleaching, fixing, water washing, and stabilization; the developed silver produced by color development is bleached with halogenation. Thereafter, any method may be used for processing, such as a development method in which color development is performed again to increase the amount of produced dye. The color developing solution used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, Alkali metal halides, benzyl alcohol, water softeners,
A thickening agent, a development accelerator, etc. can also be optionally included. Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and sodium bromide, alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, and 1-phenyl. -5-
In addition to compounds for rapid processing solutions such as mercaptotetrazole and tetrazaindene derivatives as described in Japanese Patent Publication No. 58-43735, anti-staining agents, anti-sludge agents, preservatives, interlayer effect promoters,
There are chelating agents, etc. In addition, the pH value of the color developing solution is usually 7 or more, preferably in the range of 9 to 13. Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. Representative examples of the above aminopolycarboxylic acids include the following. Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Iminodiacetic acid Glycol ether diamine tetraacetic acid Ethylenediaminetetrapropionic acid Ethylenediaminetetraacetic acid disodium salt Diethylenetriaminepentaacetic acid pentasodium salt Nitrilotriacetic acid sodium salt Bleaching solution can be used with various additives along with the above bleaching agents. It may also contain an agent. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. And, as in the case of the bleaching solution mentioned above, various other additives such as PH buffers, optical brighteners, antifoaming agents, surfactants,
Preservatives, chelating agents, stabilizers, organic solvents, etc. may be added or contained. Examples of silver halide fixing agents include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned. Processing temperatures for various processing steps other than color development of the internal latent image type photosensitive material of the present invention, such as bleach-fixing (or bleaching and fixing), as well as water washing and stabilization as necessary, are also important for rapid processing. From a point of view 30
Preferably, the reaction is carried out at a temperature of 0.degree. C. or above. The internal latent image type photosensitive material of the present invention is
No. 14834, No. 58-105145, No. 58-134634 and No. 58-18631, and Japanese Patent Application No. 58-2709 and No. 59
A stabilization treatment as an alternative to water washing, such as that shown in No.-89288, may be performed. Further, the internal latent image type silver halide emulsion used in the present invention includes those prepared by various methods. For example, convergence silver halide emulsions as described in U.S. Pat. Silver emulsion or US patent
Silver halide emulsions having silver halide grains containing polyvalent metal ions as described in US Pat. No. 3,271,157, US Pat. Silver halide emulsion in which the surface of silver halide grains is weakly chemically sensitized, or JP-A-50-8524
So-called core-shell type silver halide emulsions consisting of grains having a laminated structure as described in Japanese Patent Application Laid-open Nos. 1983-156614 and 55-127549. and 57-
Examples include silver halide emulsions described in Publication No. 79940. There is no particular limit to the amount of silver coated in the silver halide emulsion layer, but a smaller amount of silver coated is preferable from the viewpoint of speeding up development, and especially silver coated in the blue-sensitive emulsion layer (preferably all light-sensitive emulsion layers). The amount is 1.5g/ ^m2
The amount is preferably below, more preferably 1.0 g/m ² or less, and the maximum effect can be obtained at this time. Furthermore, the internal latent image type silver halide emulsion used in the present invention contains 1 mg to 10 g of a compound having an azaindene ring, a nitrogen-containing heterocyclic compound having a mercapto group, etc. per mole of silver halide. , can give more stable results with a lower minimum concentration. As the compound having an azaindene ring, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene is preferred. As the nitrogen-containing heterocyclic compound having a mercapto group, 1-phenyl-5-mercaptotetrazole is preferred. In addition, the silver halide emulsion may contain antifoggants or stabilizers such as mercury compounds, triazole compounds, azaindene compounds, benzothiazolium compounds, and zinc compounds. Various photographic additives may optionally be added to the internal latent image type silver halide emulsion applied to the present invention. For example, optical sensitizers that can be used in the present invention include cyanines, merocyanines, trinuclear or tetranuclear merocyanines, trinuclear or tetranuclear cyanines, styryls, holoporacyanines, hemicyanines, and oxonols. These optical sensitizers include basic groups such as thiazoline and thiazole, or rhodanine, thiohydantoin, oxazolidinedione, barbituric acid, and thiobarbituric acid as part of their structure as a nitrogen-containing heterocyclic nucleus. Those containing a nucleus such as acid, pyrazolone, etc. are preferred, and such nucleus can be substituted with alkyl, hydroxyalkyl, sulfoalkyl, carboxyalkyl, halogen, phenyl, cyano, or alkoxy, and can be fused with a monocyclic or heterocyclic ring. is optional. The internal latent image type silver halide emulsion used in the present invention can be supersensitized. For information on the method of supersensitization, see, for example, "Overview of the mechanism of supersensitization"
(Review of Supersensitization)
(Photographic Science and Engineering),
(PSE) Vol. 18, page 4418 (1974). Although the red-sensitive emulsion layer of the internal latent image type silver halide emulsion layer according to the present invention contains the cyan coupler of the present invention, a cyan coupler other than the present invention may also be used in combination with the red-sensitive emulsion layer. good. However, good effects can be obtained when the cyan coupler of the present invention is used in an amount of at least 5 mol % or more, preferably 10 mol % or more, and more preferably 20 mol % or more based on the total amount of cyan coupler. Further, the blue-sensitive emulsion layer and the green-sensitive emulsion layer according to the present invention can contain a yellow coupler and a magenta coupler, respectively. Yellow couplers that can be used in the present invention include closed ketomethylene compounds, active point -o-aryl substituted couplers called so-called 2-equivalent type couplers, active point -o-acyl substituted couplers,
Active point hydantoin compound substituted couplers, active point urazole compound substituted couplers, active point substituted couplers with succinimide compounds, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -o-sulfonyl substituted couplers, etc. are effective. Can be used as a yellow coupler. Specific examples of yellow couplers that can be used include U.S. Pat.
No. 3408194, No. 3551155, No. 3582322, No. 3582322, No. 3551155, No. 3582322, No.
No. 3725072, No. 3891445, West German Patent No. 1547868,
West German Application No. 2219917, West German Application No. 2261361, West German Publication No.
No. 2414006, British Patent No. 1425020, Special Publication No. 1977-
No. 10783, JP-A-47-26133, JP-A No. 48-73147,
No. 51-102636, No. 50-6341, No. 50-123342
No. 50-130442, No. 51-21827, No. 50-
No. 87650, No. 52-82424, No. 52-115219, No. 58
Examples include those described in No.-95346. Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. These magenta couplers are similar to the yellow couplers 4
Not only an equivalent type coupler but also a two-equivalent type coupler may be used. Specific examples of magenta couplers include U.S. Patent No. 2600788, U.S. Patent No. 2983608, and U.S. Patent No. 3062653.
No. 3127269, No. 3311476, No. 3419391,
Same No. 3519429, No. 3558319, No. 3582322, Same No.
No. 3615506, No. 3834908, No. 3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665,
No. 2417945, No. 2418959, No. 2424467, Japanese Patent Publication No. 1973-6031, Japanese Patent Publication No. 51-20826, No. 52-58922
No. 49-129538, No. 49-74027, No. 50-
No. 159336, No. 52-42121, No. 49-74028, No. 50
Examples include those described in No. 60233, No. 51-26541, No. 53-55122, and Japanese Patent Application No. 110943/1983. Furthermore, cyan couplers that can be used in combination in the present invention include phenol couplers, naphthol couplers, etc. that are not included in the present invention. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers include U.S. Patent No. 2369929, U.S. Patent No. 2434272, and U.S. Patent No. 2474293.
No. 2521908, No. 2895826, No. 3034892,
No. 3311476, No. 3458315, No. 3583971, No.
No. 3591383, No. 3767411, No. 3772002, No.
No. 3933494, No. 4004929, West German patent application (OLS)
No. 2414830, No. 2454329, JP-A-48-59838,
No. 51-26034, No. 48-5055, No. 51-146827,
No. 52-69624, No. 52-90932, Special Publication No. 1977-
Examples include those described in No. 11572 and the like. Couplers such as non-diffusible DIR compounds, colored magenta or cyan couplers, polymer couplers, and diffusible DIR compounds may be used in combination in the silver halide emulsion layer of the present invention and other photographic constituent layers. Regarding non-diffusible DIR compounds, colored magenta or cyan couplers, a patent application filed by the present applicant in 1982-
For polymer couplers, reference may be made to the description in Japanese Patent Application No. 193611, filed by the present applicant in Japanese Patent Application No. 172151/1983. The amount of the above coupler that can be used in the present invention is not limited, but is preferably 1 x 10 ^-3 to 5 mol, more preferably 1 x 10 ^-2 to 5 x 10 ^-1 per mol of silver.
It is. In order to incorporate the cyan coupler of the present invention into the silver halide emulsion of the present invention, if the cyan coupler of the present invention is alkali-soluble, it may be added as an alkaline solution, or it may be added as an oil-soluble solution. For example, US Pat. No. 2,322,027,
The cyan coupler of the present invention is used as a high boiling point solvent, and if necessary, a low boiling point solvent is used in combination according to the method described in the specifications of the same No. 2801170, the same No. 2801171, the same No. 2272191, and the same No. 2304940. It is preferable to dissolve it, disperse it in the form of fine particles, and add it to the silver halide emulsion. At this time, if necessary, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination. Furthermore, two or more cyan couplers of the present invention may be used in combination. Further, in detailing the preferred method of adding the cyan coupler of the present invention in the present invention, one or more types of the cyan coupler of the present invention may be added to other couplers, hydroquinone derivatives,
Along with anti-fading agents and ultraviolet absorbers, organic acid amides, carbamates, esters, ketones,
Urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, triresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n-butyl sebacate,
Tri-n-hexyl phosphate, N,N-di-
Ethyl-caprylamidobutyl, N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3-pentadecyl phenylethyl ether, 2,5-di-sec-amyl High boiling point solvents such as phenyl butyl ether, monophenyl-di-o-chlorophenyl phosphate or fluorine paraffin, and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, Nitromethane, carbon tetrachloride,
Dissolved in a low boiling point solvent such as chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or sorbitan sesquioleate and sorbitan. Mix with an aqueous solution containing a nonionic surfactant such as monolauric acid ester and/or a hydrophilic binder such as gelatin, emulsify and disperse with a high-speed rotation mixer, colloid mill, ultrasonic dispersion device, etc., and add to the silver halide emulsion. be done. In addition, the above couplers and the like may be dispersed using a latex dispersion method. The latex dispersion method and its effects are disclosed in Japanese Patent Application Laid-open Nos. 49-74538 and 51-59943.
No. 54-32552 and Research Disclosure August 1976, No. 14850, pages 77-79. Suitable latexes include, for example, styrene, acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3
-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamide-
Homopolymers, copolymers and terpolymers of monomers such as 2-methylpropanesulfonic acid and the like. The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives. For example, Research Disclosure Magazine
Antifoggants and stabilizers described in No. 17643;
Ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used. In addition to gelatin, suitable gelatin derivatives can be used as protective colloids or binders in the silver halide emulsion layer according to the present invention depending on the purpose. Suitable gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin. In addition, in the present invention, other hydrophilic binders (binders) can be included depending on the purpose, such as colloidal albumin, agar, gum arabic, dextran, alginic acid, acetyl-containing 19
cellulose derivatives such as cellulose acetate hydrolyzed to ~20%, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinylamino acetate copolymers; Polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups, polyvinylpyridine,
Contains polyvinylamine, polyaminoethyl methacrylate, polyethyleneamine, etc., and can be added to constituent layers of photographic light-sensitive materials such as emulsion layers, intermediate layers, protective layers, filter layers, and backing layers depending on the purpose. The binder may contain a suitable plasticizer, lubricant, etc. depending on the purpose. Further, the constituent layers of the internal latent image type photosensitive material according to the present invention can be hardened with any suitable hardening agent. These hardeners include chromium salts,
Zirconiums, aldehydes such as formaldehyde and mucohalogen acids, halotriazines,
Examples include polyepoxy compounds, ethyleneimine hardeners, vinyl sulfone hardeners, and acryloyl hardeners. Examples of the support for the internal latent image type photosensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflector, such as glass plates, cellulose acetate, Examples include polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and other common transparent supports may also be used. These supports are appropriately selected depending on the intended use of the photosensitive material. For coating the internal latent image type silver halide emulsion layer and other photographic constituent layers used in the present invention,
Various coating methods can be used, such as dip coating, air doctor coating, curtain coating, and hopper coating. Also, U.S. Patent No. 2761791,
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 2941898. In the present invention, the number of emulsion layers and the coating positions can be determined arbitrarily. For example, in the case of a full-color internal latent image type light-sensitive material, it consists of three emulsion layers: a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer.
Each of these photosensitive silver halide emulsion layers may consist of two or more layers. The effects of the present invention are most effective when all of these photosensitive emulsion layers are substantially composed of silver chlorobromide emulsion. In the internal latent image type photosensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and further various layers such as a filter layer, an anti-curl layer, a protective layer, an antihalation layer, etc. can be used in appropriate combination as a constituent layer. Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included. [Effects of the Invention] According to the present invention, even when processed with a low replenishment amount using a color developing solution containing the color developing agent of the present invention, there is no change in bromide ion concentration, and there is little occurrence of development fog. It is possible to provide a rapid and stable processing method for an internal latent image type photosensitive material for direct positive image formation, which can always maintain constant and appropriate photographic performance over a long period of time. [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. Incidentally, the amounts added below are per 1 m ² unless otherwise specified. Example 1 On a paper support laminated with polyethylene,
The following layers were sequentially coated from the support side to prepare internal latent image type photosensitive material samples Nos. 1 to 25. 1st layer: Cyan forming red-sensitive silver halide emulsion layer Mix and dissolve 90 g of cyan coupler (C-111), 2 g of 2,5-di-tert-octylhydroquinone, 50 g of tricresyl phosphate, 200 g of paraffin and 50 g of ethyl acetate. Then, a gelatin solution containing sodium dodecylbenzenesulfonate was added and dispersed so that the average particle size was 0.6 μm (U.S. patent
An internal latent image type silver halide emulsion (silver halide composition is shown in Table 1) (prepared by the convergence method according to Example 1 described in No. 2592250) was added, and the silver amount was 400 mg/m ² , the amount of coupler was 360 mg/m ² . 2nd layer: Intermediate layer 100 ml of a 2.5% gelatin solution containing 5 g of gray colloidal silver and 10 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate was applied to give a colloidal silver amount of 400 mg/ ^m2. . Third layer: Magenta-forming green-sensitive silver halide emulsion layer Magenta coupler, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecylsuccinimideanilino)-5-pyrazolone
100g, 2,5-di-tert-octylhydroquinone 5g, Sumilizer MDP (manufactured by Sumitomo Chemical Co., Ltd.)
50g, paraffin 200g, dibutyl phthalate 100g
Internal latent image type silver halide prepared in the same manner as the first layer by mixing and dissolving 50 g of ethyl acetate and adding a gelatin solution containing sodium dodecylbenzenesulfonate and dispersing it so that the average particle size was 0.6 μm. An emulsion (silver halide composition shown in Table 1) was added and coated so that the amount of silver was 400 mg/m ² and the amount of coupler was 400 mg/m ² . 4th layer: Yellow filter layer A 2.5% gelatin solution containing 5 g of yellow colloidal silver and 5 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate was coated so that the colloidal silver was 200 mg/ ^m2 . . 5th layer: Yellow-forming blue-sensitive silver halide emulsion layer Yellow coupler, α-'4(1-benzyl-2
-phenyl-3,5-dioxo-1,2,4-triazolidinyl)]-α-bivalyl-2-chloro-5
-[γ(2,4-di-tert-amylphenoxy)butyramide]acetanilide 120 g, 2,5-di-tert-octylhydroquinone 3.5 g, paraffin 200 g, Tinuvin (manufactured by Ciba Geigy) 100 g,
Mix and dissolve 100 g of dibutyl phthalate and 70 ml of ethyl acetate, add gelatin solution containing sodium dodecylbenzenesulfonate, and make a solution with an average particle size of 0.9 μm.
An internal latent image type silver halide emulsion prepared in the same manner as the first layer (silver halide composition is shown in Table 1) was added, and the silver amount was 400 mg/m ² .
The amount of coupler was applied at 400 mg/m ² . 6th layer: Protective layer It was applied so that the amount of gelatin was 200 mg/m ² . All of the above layers contained bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as a coating aid. Internal latent image type photosensitive material samples No. 1 to 25 shown in Table 1
After each was exposed through an optical wedge, it was processed in the next step. Processing process (38℃) Immersion (color developer) 8 seconds Color development 120 seconds (uniform exposure of the entire surface with 1 lux light for the first 10 seconds) Bleach-fixing 60 seconds Washing 60 seconds Drying 60-80℃ 120 seconds each The composition of the treatment liquid is as follows. [Color developer] Pure water 800ml Benzyl alcohol 15ml Hydroxyamine sulfate 2.0g Potassium bromide 0.6g Sodium chloride 1.0g Potassium sulfite 2.0g Triethanolamine 2.0g Color developing agent (as shown in Table 1) 0.023 mol 1-hydroxyethylidene -1,1-diphosphonic acid (60% aqueous solution) 1.5ml Magnesium chloride 0.3g Potassium carbonate 32g Kaycoll-PK-Conc
(Fluorescent brightener, manufactured by Nisso Kako Co., Ltd.) Add 2g of pure water and make 1, 20% potassium hydroxide or
Adjust the pH to 10.1 with 10% dilute sulfuric acid. [Bleach-fix solution] Pure water 550ml Ammonium salt of ethylenediaminetetraacetate 65g Ammonium thiosulfate (70% aqueous solution) 85g Sodium bisulfite 10g Sodium metabisulfite 2g Disodium ethylenediaminetetraacetate 20g Add pure water to make 1, and add ammonia Adjust the pH to 7.0 with water or dilute sulfuric acid. Separately, the potassium bromide concentration of the above color developer
The same sample as above was prepared using a color developer with the only difference being that 0.6g/ was changed to 1.5g/ and 3.5g/.
Each of Nos. 1 to 25 was developed. Sensitometry was performed on each of the obtained samples by a conventional method. The maximum density (Dmax) of the yellow dye of each sample when the potassium bromide concentration was 0.6 g/100 was set as 100, and Table 1 shows the concentration changes when the potassium bromide concentration was varied. However, for samples No. 13 to No. 25, development was completed within the color development time of 120 seconds, but for samples No. 1 to No.
For those in which development was not completed within 120 seconds, the color development time was extended until development was completed.

[Table] As is clear from the results in Table 1, sample No. 1 or
Compared to No. 12, a sample that is essentially silver chlorobromide
No. 13 to No. 25, and when the color developing agent is the exemplary compound (1) or (2) of the present invention, the bromide ion concentration in the color developer is 0.6 g/, 1.5 g/,
It can be seen that the coloring density does not change much even when the amount is changed to 3.5g/, indicating that the processing stability is high. On the other hand, in the case of the conventionally known color developing agent CD-3 or CD-6, regardless of the composition of silver halide, in both cases the bromide ion concentration in the color developing solution increases. It can be seen that there is a drawback that the color density decreases accordingly. Furthermore, Table 1
This shows that as the bromide ion concentration increases, the amount of replenishment is reduced, indicating that the amount of replenishment can be significantly reduced in the treatment of the present invention. In addition, the cyan coupler can be used as an exemplary compound of the present invention (C
-111), the exemplary compound of the present invention (C-86)
The same experiment was repeated using (C-101) and (C-101), and almost the same results were obtained. Example 2 Sample No. 17 of the internal latent image type photosensitive material of Example 1 was exposed and developed in the same manner as in Example 1 using the same processing solution. A color developing solution was prepared by changing the color developing agent as shown in Table 2 to give a potassium bromide concentration of 1.5 g/ml, and was used for processing. The color development time was varied as shown in Table 2. The treatment temperature was 38°C. The minimum density (Dmin) of the yellow dye of the obtained sample was measured and shown in Table 2.

【table】

[Table] As is clear from the results in Table 2, when the color developer uses CD-3 or CD-6 as the color developing agent, there is no large difference in the minimum density no matter how many seconds the color development time is. unacceptable. On the other hand, the color developing agent exemplified compound (1) of the present invention or
In the case of (2), when the color development processing time is 180 seconds or more, the minimum density is extremely high. However, it can be seen that when the color development time is 150 seconds or less, the development fog is rapidly improved, and favorable results similar to those obtained using CD-3 described above can be obtained. In addition, the cyan coupler can be used as an exemplary compound of the present invention (C
-111), the exemplary compound (C-2) of the present invention
The same experiment was repeated using (C-8) and (C-8), and almost the same results were obtained. Example 3 Using each of the silver halide samples No. 3 and No. 17 of Example 1, samples were prepared in which the average grain size of the silver halide grains in the blue-sensitive emulsion layer was varied as shown in Table 3. This sample was exposed to light in the same manner as in Example 1 and treated with the same processing solution as in Example 1. A color developing solution was prepared by changing the color developing agent as shown in Table 3 so that the concentration of potassium bromide was 1.5 g/ml. At 38℃
The maximum density of the yellow dye after 10 minutes of color development is assumed to be 100, and Table 3 shows the processing time (development settling time) required to reach the maximum density of 80 and the minimum yellow dye density at that time. This result shows the relationship between average particle size and development speed.

[Table] As is clear from the results in Table 3, when the silver halide is silver chlorobromide, the color developing agent is the one of the present invention, and the average particle size is 1.4 μm or less, the development convergence is extremely fast. (Achievement) time, and it can be seen that rapid development processing is possible and development fog is low. On the other hand, even with the color developing agent of the present invention, the average particle size is
When the thickness is 1.5 μm or more, the development convergence (arrival) time suddenly becomes longer and the development fog becomes higher. In addition, when the color developing agent is a color developing agent other than the one according to the present invention, even if the average particle size is small, a fast development convergence time cannot be obtained. On the other hand, when the silver halide is essentially silver iodobromide, even if the color developing agent is of the present invention, a fast development convergence time can be achieved regardless of the average grain size. I know that I can't. In addition, the cyan coupler can be used as an exemplary compound of the present invention (C
-111), the exemplary compound of the present invention (C-29)
The same experiment was repeated using (C-36) and (C-36), and almost the same results were obtained. Example 4 Using samples No. 3 and No. 17 of Example 1, the color developing agent and potassium bromide concentration in the color developer were changed in the same manner as in Example 1, and the potassium bromide concentration was
The maximum concentration (Dmax) of the yellow dye of each sample at 0.6 g/concentration was set as 100, and Table 4 shows the concentration changes when the potassium bromide concentration was varied. However, the fogging process uses 1-acetyl-2 as a fogging agent during color development instead of exposing the entire surface to light.
- phenylhydrazine [fogging agent (1)], or 1
-Formyl-2-(4-methylphenyl)hydrazine [fogging agent (2)] was added at 1 g each, and the pH of the color developer was adjusted to 12.

[Table] As is clear from the results in Table 4, even with the treatment of the present invention, the light fogging treatment is less susceptible to the influence of the bromide ion concentration. In addition, the cyan coupler can be used as an exemplary compound of the present invention (C
-111), the exemplary compound (C-14) of the present invention
The same experiment was repeated using (C-56) and (C-56), and almost the same results were obtained. Example 5 Using silver halide of sample No. 17 of Example 1,
Samples were prepared in which the cyan coupler was changed as shown in Table 5. This sample was treated with the same treatment solution as in Example 1 under the same conditions as in Example 1. The color developing solution was prepared by changing the color developing agent as shown in Table 5 so that the potassium bromide concentration was 1.5 g/ml. Next, each color developing solution was transferred to an Erlenmeyer flask and stored at 50° C. for 2 weeks while supplying water from time to time. After storage, these color developing solutions were used to repeat the same treatments as those performed before storage over time. The maximum concentration (Dmax) of the cyan dye of the obtained sample was measured, and the maximum concentration of the cyan dye treated with the color developer before storage over time was set as 100, and the concentration when processed with the color developer after storage over time was calculated. Table 5
It was shown to.

【table】

[Table] As is clear from the results in Table 5, with cyan couplers other than the present invention, the maximum concentration of cyan dye decreases after storage over time even when the color developing agent of the present invention is used, but with the cyan couplers of the present invention, the maximum concentration of cyan dye decreases after storage over time. By using a coupler and using the color developing agent of the present invention,
It is possible to effectively prevent a decrease in the maximum density of cyan dye after storage over time. Example 6 Among the color developing solutions prepared in Example 5 and stored over time, the sample used in Example 5 was processed using a color developing solution using the sulfate of exemplified compound (1) as a color developing agent. . Here, the color development time was varied as shown in Table 6, and the maximum density (Dmax) of the cyan dye of the obtained samples was measured and shown in Table 6.

[Table] As is clear from the results in Table 6, samples using comparative cyan couplers other than those of the present invention showed a significant decrease in cyan dye density during short-time processing of 150 seconds or less, but the cyan couplers of the present invention It can be seen that the cyan dye density decreases very little in the sample using 150 seconds or less.

Claims (1)

[Scope of Claims] 1. An internal latent image type silver halide color for direct positive color image formation, which has at least one photosensitive emulsion layer containing internal latent image type silver halide grains whose grain surfaces are not fogged in advance. In a method in which a photographic light-sensitive material is subjected to color development treatment after image exposure to directly form a positive color image, the silver halide emulsion in at least one light-sensitive emulsion layer is substantially a silver chlorobromide emulsion, and at least a blue-sensitive emulsion is used. The average grain size of the silver halide grains in the layer is 1.4 μm or less, and the red-sensitive emulsion layer has the following general formula [I], [] or []
An internal latent image type silver halide color photographic light-sensitive material for direct positive color image formation containing at least one cyan coupler represented by: 30℃ or higher using a color developing solution containing 10 ^-3 mol/bromide,
A method for forming a direct positive color image characterized by developing in 150 seconds or less. General formula [] In the formula, one of R and R ₁ is a hydrogen atom, the other is a linear or branched alkyl group having at least 2 to 12 carbon atoms, and X is a hydrogen atom or N-hydroxyalkyl-substituted-p-phenylenediamine It represents a group that can be separated by a coupling reaction with an oxidized product of a derivative color developing agent, and R ₂ represents a ballast group. General formula [] General formula [] In the formula, Y is -COR ₄ , [Formula] -SO ₂ R ₄ , [Formula] [Formula] -CONHCOR ₄ or -CONHSO ₂ R ₄ (However, R ₄ is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or represents a heterocyclic group, R ₅ is a hydrogen atom, an alkyl group, an alkenyl group,
It represents a cycloalkyl group, an aryl group, or a heterocyclic group, and R ₄ and R ₅ may be combined with each other to form a 5- to 6-membered heterocycle. ), R ₃ represents a ballast group, and Z represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an N-hydroxyalkyl-substituted p-phenylenediamine derivative color developing agent. 2. The method for forming a direct positive color image according to claim 1, wherein after the image exposure, a color development process is carried out after and/or while performing a full-surface exposure as a fogging process. 3. Claims 1 or 2, characterized in that the silver halide emulsion of at least one photosensitive emulsion layer is a silver chlorobromide emulsion with a silver bromide content of 90 mol% or less. A method of forming a direct positive color image as described. 4. The method for forming a direct positive color image according to any one of claims 1 to 3, characterized in that processing is performed with a color developing solution containing 1 x 10 ^-2 mol/or more of bromide. 5. The method for forming a direct positive color image according to claim 4, characterized in that processing is performed with a color developing solution containing 1.5×10 ⁻² mol/or more of bromide. 6. The method for forming a direct positive color image according to any one of claims 1 to 5, wherein the average grain size of the silver halide grains in at least the blue-sensitive emulsion layer is 1.0 μm or less. 7 N-Hydroxyalkyl-substituted-p-phenylenediamine derivative is 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline salt
7. The method for forming a direct positive color image according to any of item 6. 8. Direct positive color according to any one of claims 1 to 7, characterized in that the color photographic material is processed continuously with a replenishment amount of color developer of 250 m/m ² or less. How images are formed. 9. Direct positive color according to any one of claims 1 to 8, characterized in that the color photographic material is processed with a replenishment amount of color developing solution of 200 ml/m ² or less during continuous processing. How images are formed.