JPH0379698B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a color development processing method for silver halide color photographic light-sensitive materials (hereinafter referred to as light-sensitive materials), and more specifically, the present invention relates to a method for color development processing of silver halide color photographic light-sensitive materials (hereinafter referred to as light-sensitive materials), and more specifically, the present invention relates to a method for color development processing of silver halide color photographic light-sensitive materials (hereinafter referred to as light-sensitive materials). The present invention relates to a new processing method that has less dependence and processing time dependence, does not impair speed, has excellent photofading resistance, and can obtain dye images with high storage stability, and has little magenta fog when mixed with heavy metal ions. In particular, the present invention relates to a processing method that requires a small amount of replenishment and has high processing stability. [Prior Art] Processing of light-sensitive materials basically consists of two steps: color development and desilvering, and desilvering consists of bleaching and fixing steps or bleach-fixing steps. In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps. In color development, the exposed silver halide is reduced to silver, and at the same time the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. During this process, halogen ions generated by reduction of silver halide are eluted into the developer and accumulated. Additionally, components such as inhibitors contained in the silver halide photographic light-sensitive material are also eluted into the color developing solution and accumulated. In the desilvering step, silver produced by development is bleached with an oxidizing agent, and then all silver salts are removed from the photographic material as soluble silver salts with a fixing agent. A one-bath bleach-fixing method is also known in which the bleaching step and the fixing step are carried out simultaneously. As mentioned above, development inhibitors accumulate in color developing solutions when photographic light-sensitive materials are developed, but on the other hand, color developing agents and benzyl alcohol are consumed or accumulated in the photographic light-sensitive materials and taken out. The concentration of the components decreases. Therefore, in a development method in which a large amount of silver halide photographic light-sensitive material is continuously processed using an automatic processor, etc.,
In order to avoid changes in development finish characteristics due to changes in component concentration, a means is required to maintain the components of the color developer within a constant concentration range. 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 amount of overflow liquid, the so-called concentrated and low filling method has been widely used, in which these replenishers are concentrated and refilled in small amounts, and another method is to add a regenerant to the overflow liquid and use it again as a replenisher. It has been proposed and put into practical use. [Problems to be Solved by the Invention] All of these methods substantially reduce the amount of replenishment. If the amount of replenishment is extremely reduced, the concentration of organic inhibitors and halogen ions eluted into the developer will change significantly even if there is a slight error in the amount of replenishment, and the concentration will be affected by evaporation. The concentration of the above-mentioned fatigue deposits usually increases. For example, when the halogen ion concentration increases, the development reaction is suppressed or the legs of the characteristic curve are further suppressed, resulting in a problem of high contrast. To avoid this, halogen ions are removed from the overflow solution using an ion exchange resin or electrodialysis, and a regenerating agent is added to compensate for the missing components generated during development and lost during regeneration processing, and the solution is regenerated as a replenisher. A method is proposed for use. 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. The difference between weekends when the number of orders decreases, and the high season and off-season can be as large as 1:5, and the composition of the processing solution can vary widely because it is also affected by evaporation and differences in the amount of replenisher. It has some drawbacks. Therefore, in low-replenishment processing and recycling methods, efforts are made to quantitatively analyze the components and make the composition constant each time the product is recycled, making it difficult for photo labs and mini-labs without special skills to carry out these regeneration processing and low-replenishment processing. There are many things like that. These problems are mainly caused by changes in bromide ions, which are development inhibitors. It has also been proposed to reduce fluctuations in bromide ion concentration due to quantity errors (Japanese Patent Application No. 1983-
(See No. 173189, No. 59-205540, etc.) It is assumed that these problems can be solved by improving developability by reducing the average grain size of silver halide in photographic materials or by reducing the amount of silver coated, but conventional developing agents cannot In a color developing solution using a certain 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, when the developability is improved, it is affected by the bromide ion concentration in the developer. The result is the opposite of what was expected: the process becomes easier and the processing stability is impaired. However, it is an important issue to improve processing stability while shortening processing time. Conventionally, in color paper processing consisting essentially of a silver chlorobromide emulsion, color development was performed at 33°C for 3 minutes and 30 seconds - bleach-fixing at 33°C for 1 minute and 30 seconds - washing with water for 3 minutes (or stabilization for 3 minutes) - drying. It is becoming. The total processing time is generally about 8 minutes, but 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 point of view of shortening delivery times. ing. 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 ions, which are inhibitors, and the concentrations of sulfur 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 agent, which has been used for a long time as the most suitable agent for developing silver chlorobromide emulsions, has low hydrophilicity.
Penetration of color developing agents into photosensitive materials is slow, and various penetrants have been studied to speed up the penetration.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 color development, a method is known in which a color developing agent is incorporated into a light-sensitive material in advance. For example, a method is known in which a color developing agent is converted into a metal salt and incorporated (US Pat. No. 3,719,492), but with this method, the raw storage of the photosensitive material is poor, and the material may be damaged before use, or the color developing agent may be further removed from the color developing agent. The drawback was that it was easy to get foggy at times. 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. Furthermore, when the color developing agent is directly incorporated, 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 was hot. Furthermore, it is known that 3-pyrazolidones are added to a black and white developer containing a developer such as hydroquinone to accelerate development (e.g. LF
Written by A. Mason, Photographic Processing
Chemistry 103-107, Focal Press, 1966
Year). The fact that this compound is incorporated into photosensitive materials is
It is described in British Patent No. 767704, but the technology described in the patent specification incorporates it into a black-and-white photosensitive material or a reversal color photosensitive material, and its purpose is to promote only black-and-white development. Furthermore, in JP-A No. 53-52422, 3-pyrazolidones are added for the purpose of preventing a decrease in sensitivity in an unexposed state of a color photosensitive material containing a 2-equivalent magenta coupler having an oxy-type organic split-off group at its active site. However, these techniques are not suitable for speeding up color development processing by stabilizing it with low replenishment processing. In addition, as a method for speeding up color development using a conventionally known accelerator, US Pat. No. 2,950,970
No. 2515147, No. 2496903, No. 4038075,
British Patent No. 4119462, British Patent No. 1430998, British Patent No. 1455413,
JP-A No. 53-15831, No. 55-62450, No. 55-
Compounds described in Japanese Patent Publication No. 62451, No. 55-62452, No. 55-62453, Japanese Patent Publication No. 51-12322, No. 55-49728, etc. have been investigated, but most of the compounds have insufficient promoting effects. Moreover, compounds exhibiting a high degree of accelerating effect not only have the drawback of forming fog, but are also unsuitable as a method for improving processing stability. Furthermore, the provision of a silver halide emulsion layer which is substantially non-photosensitive in a light-sensitive material to accelerate development is disclosed in Japanese Patent Application Laid-open No. 50-23225, Japanese Patent Application Publication No. 56-14236, British Patent No. 1378577, and OLS 2622922. 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 promote development. Not only was the effect of accelerating development small, but even though it was effective against fluctuations in iodide ion concentration, no process stabilization effect was obtained at all against fluctuations in bromide ion concentration. On the other hand, 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 a high developing activity and can speed up the development, it is known that the coloring dye after processing has low fading resistance and is therefore undesirable. On the other hand, 3
-Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline-di-p-toluenesulfonate does provide rapidity, but it does not provide stable bromide ion concentration, and the photo after treatment It has the disadvantage that a yellow stain is significantly generated in the unexposed areas of the photosensitive material, and especially when processed for a short time, the color developing agent remains and causes a rough stain, so it cannot be used 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 monohydra, 3-methyl-4-amino-N-β-hydroxyethylaniline sulfate, etc., in Photographic Science and Engineering Vol.8, No.3.5-June, 1964 Year,
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, there are few color developing agents that can provide substantial development activity of a silver chlorobromide emulsion and have excellent storage stability of dye images; generally, 3-methyl-4-amino-N-ethyl-N-β- Methanesulfonamidoethylaniline sulfate was used with benzyl alcohol to achieve this objective. However, in this case, as described above, it is susceptible to changes in bromide ion concentration. Further, in the concentrated low replenishment process in which the amount of replenisher is reduced, another problem is an increase in the contamination and accumulation of other processing liquid components.
This is because the rate at which the tank liquid is replaced with replenisher becomes lower due to a decrease in the amount of replenishment, and also because the period of use of the liquid becomes longer. 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 contaminant components that accumulate, thiosulfate ion, which is a fixing agent, accelerates development. That is, this problem occurs particularly when bleach-fixing is performed directly after color development. In particular, by promoting the shoulder of the photographic characteristic curve, a remarkable increase in contrast is produced. 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 takes place at 30℃
This will be greatly promoted. The generation of ammonia ions, like thiosulfate ions, has the disadvantage of accelerating physical development and increasing contrast. 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. Therefore, 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. To provide a rapid and stable processing method for a silver halide color photographic light-sensitive material in which colored dyes and uncolored areas do not fade or change color even after long-term storage. As a result of various studies to achieve the above-mentioned first object of the present invention, the present inventor succeeded in discovering a unique color developing agent that is almost unaffected by the bromide ion concentration when developing a specific silver halide. Although the storage stability of the resulting coloring dye was greatly improved, the following problems were encountered. That is,
When using 5-pyrazolone magenta couplers, which have been widely used in the past, there is a drawback that magenta fog, which is thought to be caused by decomposition products of hydroxylamine, tends to occur in unexposed areas. It was determined as a result of the examination. Therefore, we further investigated ways to solve this problem. [Means for Solving the Problem] As a result, in a method for developing a silver halide color photographic light-sensitive material, the silver halide emulsion in at least one light-sensitive emulsion layer is substantially a silver chlorobromide emulsion. , the membrane swelling rate T1/2 of the binder is
30 seconds or less, and a silver halide color photographic light-sensitive material containing a magenta coupler represented by the following general formula [] in the green-sensitive emulsion layer is used as a color-forming material containing an N-hydroxyalkyl-substituted p-phenylenediamine derivative. It has been found that the above object can be achieved by developing at a temperature of 30° C. or higher and 150 seconds or less using a developer. General formula [] In the formula, Z represents an atomic group necessary to form a five-membered ring consisting of a carbon atom or a nitrogen atom, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. The present inventor has discovered that when developing a color photographic light-sensitive material using an emulsion containing a specific silver halide, i.e., silver chlorobromide (particularly silver bromide content of 90 mol% or less), the color developing agent is N-hydroxyalkyl. We have found the surprising fact that only when substituted p-phenylenediamine derivatives are used, the resulting dye density hardly changes even if the bromide ion concentration changes. The above characteristics of this color developing agent include silver iodide.
This cannot be achieved with color photographic materials that use silver iodobromide emulsions containing 0.5 mol% or more, and this type of color developing agent has traditionally been used exclusively for developing silver iodobromide emulsions. This is unexpected, especially the fact that when developing a color photographic material using a substantial silver chlorobromide emulsion, the development speed is not delayed even if the bromide ion concentration is greatly increased. This is not something that can be understood from the oxidation-reduction potential or half-wave potential of common color developing agents, and it is surprising that this cannot occur unless an optimal balance between development speed and coupling speed is maintained. It happened. 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 it can be developed under a high bromide ion concentration, the amount of replenishment can be greatly reduced in the case of continuous processing, and the processing stability is extremely high. In particular, it was found that there is a drawback that the photofading property is reduced. The storage stability of dye images, especially in the case of print materials, is critical and has become a major obstacle. The inventors of the present invention made further efforts to solve this problem, and found that this problem occurs not because the storage stability of the dye itself is low, but because the color developing agent tends to remain in the color photographic material. We found that this problem could be solved by shortening the development time. However, shortening the color development time cannot be achieved unless the development processability of color photographic materials is sufficiently improved.
Although it cannot be absolutely shortened, in order to achieve low replenishment and processing stability without impairing the storage stability of the dye image, processing at a temperature of 30°C or higher and within 150 seconds using the color developing solution of the present invention is recommended. I found out that it is a condition to do so. In this case, if conventional photographic materials are used as they are, the problem arises that developing time is insufficient and sufficient photographic images cannot 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. The silver halide emulsion is substantially a silver chlorobromide emulsion, and the film swelling rate of the binder is T1/2.
The developing speed of a color photographic light-sensitive material whose temperature is 30 seconds or less is improved by processing it with a developer containing an N-hydroxyalkyl-substituted p-phenylenediamine derivative, and this color photographic light-sensitive material is heated at temperatures of 30 seconds or less
It was only through rapid color development within a range of 150 seconds or less that the object of the present invention was successfully achieved without impairing the stability of the dye image. As used herein, "substantially silver chlorobromide emulsion"
This 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. 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 hydrophilic binder used to coat silver halide in color photographic light-sensitive materials is usually gelatin, but high molecular weight polymers may also be used, and if the film swelling rate T1/2 is less than 30 seconds, Rather, the film swelling rate T1/2 of the binder can be measured according to any method known in this technical field, for example, A. Green Photo. Sci.
It can be measured by using a swell meter (swell meter) of the type described in Eng. Vol. 19, No. 2, pages 124-129, and T1/2 can be measured by color development at 30°C.
Maximum swelling between membranes reached when treated for 3 minutes and 30 seconds
90% is defined as the saturated film thickness, and is defined as the time it takes to reach 1/2 of this film thickness (see Figure 1). The binder of the photographic constituent layer used in the silver halide color photographic light-sensitive material of the present invention has a swelling rate T1/2 of 30 seconds or less, and the smaller the swelling rate, the more preferable it is.
If the lower limit is too small, the film will not be hardened and failures such as scratches will easily occur, so the lower limit is preferably 2 seconds or more.
Particularly preferably, the time is 20 seconds or less, most preferably 15 seconds or less. If the time is longer than 30 seconds, not only will the storage stability of the dye image be low, but also sufficient dye formation will not be obtained within 150 seconds. The membrane swelling rate T1/2 can be adjusted by the amount of hardener used. In the present invention, when the color photographic material of the present invention is continuously processed with a replenishment amount of 250 ml/m ² or less, the desired effects of the present invention are well exhibited,
Furthermore, it is particularly good when the amount is 200ml/ ^m2 or less,
Furthermore, it is particularly good when it is between 20 and 180 ml/m ² . At least one of the light-sensitive emulsion layers of the silver halide color photographic light-sensitive material processed according to the present invention may consist essentially of a silver chlorobromide emulsion;
Preferably, all of the light-sensitive emulsion layers consist of a silver chlorobromide emulsion. The silver chlorobromide has a silver bromide content of 90 mol% or less, preferably 70 mol% or less, since the smaller the mol% of silver bromide, the more sufficient color formation can be obtained even in a short color development time. The above is the most preferable result. Furthermore, the smaller the amount of silver coated, the more preferable it is because there is no delay in development due to an increase in bromide and sufficient dye formation can be achieved in a ^short time.
The maximum effect is obtained when the amount is 0.8 g/m ² or less. Color development processing is carried out at 30°C or higher and 150 seconds or less, preferably at 33°C or higher and 120 seconds or less, most preferably at 35°C or higher and 90 seconds or less;
When processing for more than 150 seconds, the storage stability of the dye deteriorates. In particular, processing time is more important than temperature; if the processing time exceeds 150 seconds, the photofading property of the cyan dye increases significantly, which is undesirable. The processing temperature is raised to complete the development in a short time rather than to maintain the storage stability of the dye, and it is preferable that the processing temperature is higher than 30°C and lower than 50°C, since the processing time can be shortened, and 33°C is particularly preferable. ℃ or more and 48℃ or less,
Most preferably, the treatment is performed at a temperature of 35°C or higher and 43°C or lower. An effective developing agent in the present invention is a quaternary ammonium salt of an N-hydroxyalkyl-substituted p-phenylenediamine compound, particularly one that can be represented by the following general formula. In the formula, R 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 ₂ is a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms. is an alkyl group having ₁ to 4 carbon atoms which may have a hydroxyl group, and A is an alkyl group having at least one hydroxyl group and which may have a branch. group, more preferably It is. R ₁ , R ₅ , and R 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 at least one of R ₄ , R ₅ , and R ₆ represents a hydroxyl group. Or it is 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, Journal of American Chemical Society, Vol. 73,
It can be easily synthesized by the method described in Section 3100 (1951). The color developing solution of the present invention has a bromide ion concentration of 5×
The amount is preferably 10 ^-3 mol or more, but in the present invention, the higher the bromide, the lower the amount of bromide to be replenished. In conventional development methods, bromide suppresses the development reaction, and the lower the bromide content, the better.However, in the combination of the color photographic light-sensitive material and developer of the present invention, the higher the bromide content, the more preferable it is, and the purpose of the present invention can be achieved more effectively. be done. In other words, in the present invention, the amount of replenishment can be reduced because it is less susceptible to bromide. The amount of bromide is preferably 1 x 10 ^-2 mol or more, particularly preferably 1.5 x 10 ^-2 mol or more, and if the bromide ion concentration is too high, development will be inhibited and the bromide ion concentration will start to have an effect ^. More than mol is not preferable. Note that the concentration of chloride has no effect. In the present invention, the replenishment amount of color developer is 250
The desired effect of the present invention is well achieved when the treatment is carried out at ml/m ² or less, and it is especially preferably used at 200 ml/m ² or less. The color photographic material of the present invention has a blue-sensitive emulsion layer,
In a multilayer color photographic light-sensitive material having three or more layers including each of a green-sensitive emulsion layer and a red-sensitive emulsion layer, 1/2 of the time until the film reaches its maximum swelling time, that is, the film swelling rate T1/2, is 30 seconds or less. The maximum effect is achieved when the thickness is 14μm or less when dry,
The thickness is preferably 13 μm or less, particularly preferably 12 μm or less, but in either case T1/2 is preferably 30 seconds or less. The pyrazolotriazole magenta coupler of the present invention will be described in detail below. Next, the present invention will be specifically explained. The above general formula according to the present invention [] General formula [] In the magenta coupler represented by, Z represents an atomic group necessary to form a five-membered ring consisting of a carbon atom or a nitrogen atom, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. Examples of the substituent represented by R include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group,
Sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group,
Aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group,
alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group,
Aryloxycarbonyl group, alkylthio group,
Examples include arylthio group and heterocyclic thio group. Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred. The alkyl group represented by R has 1 to 1 carbon atoms.
32, alkenyl groups, alkynyl groups with 2 to 32 carbon atoms, cycloalkyl groups, cycloalkenyl groups with 3 to 12 carbon atoms, especially 5 to 7 carbon atoms
Preferred are alkyl groups, alkenyl groups,
Alkynyl groups may be linear or branched. In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds] In addition to residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a hetero atom {specifically, hydroxy, alkoxy, aryloxy, heterocycles substituted via an oxygen atom such as oxy, siloxy, acyloxy, carbamoyloxy;
Nitro, amino (including dialkylamino, etc.),
Those substituted through a nitrogen atom such as sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, alkylthio,
Those substituted via a sulfur atom such as arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl, and those substituted via an adjacent atom such as phosphonyl, etc.}]. Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1-hexylnonyl group, 1,1'-dipentylnonyl group, 2-chloro-t-butyl group,
Trifluoromethyl group, 1-ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3- m-butanesulfonaminophenoxypropyl group, 3-4'-{α-[4″(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino}phenylpropyl group, 3-{4′-[α-
(2″,4″-di-t-amylphenoxy)butanamide]phenyl}-propyl group, 4-[α-(o-
chlorophenoxy) tetradecaneamide phenoxy] propyl group, allyl group, cyclopentyl group,
Examples include cyclohexyl group. The aryl group represented by R is preferably a phenyl group, and may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.). Specifically, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amyl phenyl group, 4
-tetradecanamide phenyl group, hexadecyloxyphenyl group, 4'-[α-(4''-t-butylphenoxy)tetradecanamide] phenyl group, etc. The heterocyclic group represented by R is 5- A 7-membered group is preferable, and may be substituted or condensed. Specific examples thereof include 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group. Examples of the acyl group represented by R include acetyl group, phenylacetyl group, dodecanoyl group, α
-2,4-di-t-amylphenoxybutanoyl group and other alkylcarbonyl groups, benzoyl groups, 3
Examples include arylcarbonyl groups such as -pentadecyloxybenzoyl group and p-chlorobenzoyl group. Examples of the sulfonyl group represented by R include a methylsulfonyl group, an alkylsulfonyl group such as a dodecylsulfonyl group, an arylsulfonyl group such as a benzenesulfonyl group, and a p-toluenesulfonyl group. The sulfinyl group represented by R includes ethylsulfinyl group, octylsulfinyl group, 3-
Alkylsulfinyl group such as phenoxybutylsulfinyl group, phenylsulfinyl group, m-
Examples include arylsulfinyl groups such as pentadecyl phenylsulfinyl groups. The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group,
Examples thereof include alkoxyphosphonyl groups such as octyloxyphosphonyl groups, aryloxyphosphonyl groups such as phenoxyphosphonyl groups, and arylphosphonyl groups such as phenylphosphonyl groups. The carbamoyl group represented by R is an alkyl group,
Aryl groups (preferably phenyl groups) may be substituted, for example, N-methylcarbamoyl groups, N,N-dibutylcarbamoyl groups, N-(2
-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group,
N-{3-(2,4-di-t-amylphenoxy)
propyl}carbamoyl group, and the like. The sulfamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-propylsulfamoyl group, an N,N-diethylsulfamoyl group,
Examples include N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, and N-phenylsulfamoyl group. Examples of the spiro compound residue represented by R include spiro[3.3]heptan-1-yl. Examples of the bridged carbonized compound residue represented by R include bicyclo[2,2.1]heptan-1-yl, tricyclo[3.3.1.1 ^3,7 ]decane-1-yl, 7,7
-dimethyl-bicyclo[2.2.1]heptane-1-
Ile et al. The alkoxy group represented by R may be further substituted with the substituents listed above for the alkyl group, such as methoxy group, propoxy group, 2-
Ethoxyethoxy group, pentadecyloxy group, 2
-dodecyloxyethoxy group, phenethyloxyethoxy group and the like. The aryloxy group represented by R is preferably phenyloxy, and the aryl nucleus may be further substituted with the substituents or atoms listed above for the aryl group, such as phenoxy group, p-
Examples include t-butylphenoxy group and m-pentadecylphenoxy group. The heterocyclic oxy group represented by R is 5 to 7
Preferably, the heterocycle has a substituent, for example, 3,
Examples include 4,5,6-tetrahydropyranyl-2-oxy group and 1-phenyltetrazole-5-oxy group. The siloxy group represented by R may be further substituted with an alkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like. The acyloxy group represented by R includes, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-chloroacetyloxy group, etc. , benzoyloxy group, etc. The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, an N-phenylcarbamoyloxy group, etc. Can be mentioned. The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethylamino group, anilino group, m
-chloroanilino group, 3-pentadecyloxycarbonylanilino group, 2-chloro-5-hexadecaneamideanilino group, and the like. As the acylamino group represented by R, an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group)
etc., which may further have a substituent, specifically an acetamide group, an α-ethylpropanamide group, an N-phenylacetamide group, a dodecanamide group, a 2,4-di-t-amylphenoxylene group, etc. Examples include cyacetamide group, α-3-t-butyl 4-hydroxyphenoxybutanamide group, and the like. Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent. Specifically, methylsulfonylamino group, pentadecylsulfonylamino group, benzenesulfonamide group, p-toluenesulfonamide group, 2-
Examples include methoxy-5-t-amylbenzenesulfonamide group. The imide group represented by R may be an open-chain one,
It may be cyclic and may have a substituent, such as a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutarimide group, and the like. The ureido group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group,
Examples include N-methyl-N-decylureido group, N-phenylureido group, and Np-tolylureido group. The sulfamoylamino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino group, N-methylsulfamoyl Examples include an amino group and an N-phenylsulfamoylamino group. The alkoxycarbonylamino group represented by R may further have a substituent, such as a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group, and the like. The aryloxycarbonylamino group represented by R may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group. The alkoxycarbonyl group represented by R may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. etc. The aryloxycarbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-pentadecyloxyphenoxycarbonyl group, etc. It will be done. The alkylthio group represented by R may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a phenethylthio group, and a 3-phenoxypropylthio group. The arylthio group represented by R is preferably a phenylthio group and may further have a substituent, such as a phenylthio group, p-methoxyphenylthio group, 2
-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, p-acetaminophenylthio group and the like. The heterocyclic thio group represented by R is 5 to 7
A membered heterocyclic thio group is preferred, and may further have a condensed ring or a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-triazole-6-thio group. Examples of substituents that can be removed by reaction with the oxidized product of the color developing agent represented by and substituent groups. In addition to carboxyl groups, examples of groups substituted via a carbon atom include, for example, the general formula (R ₁ ' has the same meaning as the above R, Z' has the same meaning as the above Z, R ₂ ' and R ₃ ' are hydrogen atoms, aryl groups,
Represents an alkyl group or a heterocyclic group. ), a hydroxymethyl group, and a triphenylmethyl group. Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups,
Examples include alkoxyoxalyloxy groups. The alkoxy group may further have a substituent,
Examples include ethoxy group, 2-phenoxyethoxy group, 2-cyanoethoxy group, phenethyloxy group, p-chlorobenzyloxy group, and the like. The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent. Specifically, phenoxy group, 3-methylphenoxy group, 3-dodecylphenoxy group, 4
-methanesulfonamidophenoxy group, 4-[α
-(3′-pentadecylphenoxy)butanamide]
Phenoxy group, hexidecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-naphthyloxy group, p
-methoxyphenoxy group and the like. The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, which may be a condensed ring or may have a substituent. in particular,
Examples include 1-phenyltetrazolyloxy group and 2-benzothiazolyloxy group. Examples of the acyloxy group include acetoxy groups, alkylcarbonyloxy groups such as butanoloxy groups, alkenylcarbonyloxy groups such as cinnamoyloxy groups, and arylcarbonyloxy groups such as benzoyloxy groups. Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group. Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group. Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group. Examples of the alkyloxalyloxy group include a methyloxalyloxy group. Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group. Examples of the group substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group. As the alkylthio group, butylthio group, 2
-cyanoethylthio group, phenethylthio group, benzylthio group, etc. The arylthio group includes phenylthio group, 4
-Methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidephenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t-butylphenylthio group, etc. can be mentioned. Examples of the heterocyclic thio group include 1-phenyl-1,2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group. Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group. Examples of the group substituting via the nitrogen atom include the general formula

Examples include those represented by the formula. Here, R ₄ ′ and R ₅ ′ are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group,
It represents an aryloxycarbonyl group or an alkoxycarbonyl group, and R ₄ ' and R ₅ ' may be combined to form a heterocycle. However, R ₄ ′ and R ₅ ′ are not both hydrogen atoms. The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, an acylamino group, and a sulfonamide group. group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamino group, aryloxycarbonylamino group, hydroxyl group, carboxyl group, cyano group, and a halogen atom.
Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-ethylhexyl group.
-chloroethyl group. The aryl group represented by R ₄ ' or R ₅ ' has 6 to 32 carbon atoms, and is particularly preferably a phenyl group or a naphthyl group. The aryl group may have a substituent, and the substituents include the above. Examples of substituents for the alkyl group represented by R ₄ ' or R ₅ ' include those listed above and an alkyl group. Specific examples of the aryl group include phenyl group, 1-naphthyl group,
A 4-methylsulfonylphenyl group is mentioned. The heterocyclic group represented by R ₄ ′ or R ₅ ′ is 5 to
A 6-membered ring is preferred, and may be a fused ring,
It may have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-furyl group, 2-quinolyl group, 2-pyrimidyl group,
-benzothiazolyl group, 2-pyridyl group, etc. The sulfamoyl group represented by R ₄ ' or R ₅ ' includes N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, These alkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group, N
-dodecylsulfamoyl group and N-p-tolylsulfamoyl group. Examples of the carbamoyl group represented by R ₄ ' or R ₅ ' include N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-diarylcarbamoyl group, etc. The alkyl group and aryl group may have the substituents listed for the alkyl group and aryl group. Specific examples of the carbamoyl group include N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, Np-cyanophenylcarbamoyl group, and Np-tolylcarbamoyl group. Examples of the acyl group represented by R ₄ ′ or R ₅ ′ include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. You may do so. Specific examples of the acyl group include hexafluorobutanoyl group,
Examples include 2,3,4,5,6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthoyl group, and 2-furylcarbonyl group. The sulfonyl group represented by R ₄ ′ or R ₅ ′ is
Alkylsulfonyl group, arylsulfonyl group,
A heterocyclic sulfonyl group may be mentioned, which may have a substituent, and specific examples include an ethanesulfonyl group, a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, a p-chlorobenzenesulfonyl group, etc. . The aryloxycarbonyl group represented by R ₄ ' or R ₅ ' may have any of the substituents listed above for the aryl group, and specific examples thereof include phenoxycarbonyl group and the like. The alkoxycarbonyl group represented by R ₄ ' or R ₅ ' may have a substituent listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, and a benzyloxycarbonyl group. etc. The heterocycle formed by combining R ₄ ' or R ₅ ' is preferably a 5- to 6-membered ring, and may be saturated or unsaturated, and may or may not have aromaticity. It may also be a fused ring. Examples of the heterocycle include N-phthalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-dioxoxazolidinyl group, 2- N-1,1-dioxo-3-
(2H)-oxo-1,2-benzthiazolyl group,
1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-pyrazolidinyl group, 1-piperidinyl group, 1-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1-indolyl group,
1-isoindolinyl group, 2-isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-benzimidazolyl group, 1-(1,
2,4-triazolyl) group, 1-(1,2,3-
triazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,
3,4-tetrahydroquinolyl group, 2-oxo-
Examples include 1-pyrrolidinyl group, 2-1H-pyridone group, phthaladione group, 2-oxo-1-piperidinyl group, and these heterocyclic groups include alkyl groups,
Aryl group, alkyloxy group, aryloxy group, acyl group, sulfonyl group, alkylamino group, arylamino group, acylamino group, sulfonamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group , an aryloxycarbonyl group, an imide group, a nitro group, a cyano group, a carboxyl group, a halogen atom, or the like. Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned. In addition, the general formula [] and the general formula [] ~
Substituents on the heterocycle in [] (for example, R,
R ₁ ~ R ₈ ) is When it has a part (here R″, X and Z″ are synonymous with R, X, Z in the general formula []),
Although it forms a so-called screw type coupler, it is of course included in the present invention. Further, the ring formed by Z, Z', Z'' and Z ₁ described below may be further fused with another ring (for example, a 5- to 7-membered cycloalkene). For example, in the general formula [] R ₅ and R ₆ are the general formula []
In, R ₇ and R ₈ may be bonded to each other to form a ring (eg, 5- to 7-membered cycloalkene, benzene). What is represented by the general formula [] is more specifically represented by, for example, the following general formulas [] to []. General formula [] General formula [] General formula [] General formula [] General formula [] General formula [] In the general formulas [] to [], R ₁ to R ₈ and X have the same meanings as R and X described above. Also, preferred among the general formulas [] are those represented by the following general formula []. General formula [] In the formula, R ₁ , X and Z ₁ are R in the general formula [],
Synonymous with X and Z. Among the magenta couplers represented by the general formulas [] to [], particularly preferred are the magenta couplers represented by the general formula []. In addition, in photosensitive materials for positive printing, the general formula [] ~
Regarding the substituents on the heterocycle in [],
In the general formula [], R is also the general formula []
In ~[], it is preferable that R ₁ satisfies the following condition 1, more preferably it satisfies the following conditions 1 and 2, and it is particularly preferable that it satisfies the following conditions 1, 2 and 3. . Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2: Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom. Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds. The most preferred substituents R and R ₁ on the heterocycle are those represented by the following general formula []. General formula [] In the formula, R ₉ , R ₁₀ and R ₁₁ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, and a sulfinyl group. , phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group , acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group represents,
At least two of R ₉ , R ₁₀ and R ₁₁ are not hydrogen atoms. Also, two of the above R ₉ , R ₁₀ and R ₁₁ , for example R ₉
and R ₁₀ may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R ₁₁ may be further bonded to the ring to form a bridged hydrocarbon compound residue. You may. The groups represented by R ₉ to _{R 11} may have a substituent, and specific examples of the groups represented by R ₉ to R ₁₁ and the substituents that the group may have are the same as those mentioned above. Specific examples of the group represented by R in formula [] and substituents are listed. Also, for example, a ring formed by combining R ₉ and R ₁₀ and
Specific examples of the bridged hydrocarbon compound residue formed by R ₉ to _{R 11} and the substituents it may have include cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in the above general formula []. Specific examples of bridged hydrocarbon compound residues and their substituents are listed. Among the general formulas [], (i) two of R ₉ to R ₁₁ are alkyl groups, (ii) one of R ₉ to R ₁₁ , for example R ₁₁ , is a hydrogen atom and , when the other two R ₉ and R ₁₀ combine to form a cycloalkyl with the root carbon atom. Further preferred among (i) is the case where two of R ₉ to _{R 11} are alkyl groups and the other one is a hydrogen atom or an alkyl group. Here, the alkyl and cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and the substituent thereof represented by R in the general formula []. Specific examples include: In addition, substituents that the ring formed by Z in general formula [] and the ring formed by Z ₁ in general formula [] may have, and general formulas [] ~
R ₂ to _{R 8} in [] are the following general formula []
The one represented by is preferable. General formula [] -R ¹ -SO ₂ -R ₂ In the formula, R ¹ represents alkylene, and R ² represents alkyl, cycloalkyl or aryl. The alkylene represented by R ¹ preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and it does not matter whether it is straight chain or branched. Further, this alkylene may have a substituent. Examples of the substituent include those shown as the substituent that the alkyl group may have when R in the above general formula [] is an alkyl group. Preferred substituents include phenyl. Preferred specific examples of alkylene represented by R ¹ are shown below. −CH ₂ CH ₂ CH ₂ −,

【formula】

【formula】

【formula】

[Formula] −CH ₂ CH ₂ CH ₂ CH ₂ −,

【formula】

【formula】

[Formula] The alkyl group represented by R ² may be linear or branched. Specifically, methyl, ethyl, propyl, iso-
Propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 2-hexyldecyl, and the like. The cycloalkyl group represented by R ² is 5-
A 6-membered one is preferred, such as cyclohexyl. Alkyl and cycloalkyl represented by R ² may have a substituent, examples of which include the above-mentioned
Examples of substituents for R ¹ include those exemplified. Specifically, the aryl represented by R ² is:
Examples include phenyl and naphthyl. The aryl group may have a substituent. Examples of the substituent include linear or branched alkyl, as well as those exemplified as the substituent for R ¹ above. Moreover, when there are two or more substituents, those substituents may be the same or different. Among the compounds represented by the general formula [], particularly preferred are those represented by the following general formula [XI]. General formula [XI] In the formula, R and X are synonymous with R and X in the general formula [], and R ¹ and R ² are R ¹ and
Synonymous with R ² . In addition, for negative photosensitive materials, the general formula []
Regarding the substituents on the heterocycle in ~[], it is preferable that R in the general formula [] and R ₁ in the general formula []~[] satisfy the following condition 1, and more preferably the following: Condition 1
and 2 are satisfied. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2 The carbon atom has at least 2 hydrogen atoms.
Individually connected or not connected at all. The most preferred substituents R and R ₁ on the heterocycle are those represented by the following general formula [XII]. General formula [XII] R ₁₂ −CH ₂ − In the formula, R ₁₂ is a hydrogen atom, a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group,
Cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue,
Bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group. The group represented by R ₁₂ may have a substituent, and specific examples of the group represented by R ₁₂ and the substituents that the group may have include the above-mentioned general formula []
Specific examples of the group represented by R and substituents are listed. Further preferred as R ₁₂ is a hydrogen atom or an alkyl group. Specific examples of compounds used in the present invention are shown below. Moreover, the synthesis of the coupler is carried out in the Journal of
Journal of the Chemical Society
Chemical Society), Perkin I
(1977), 2047-2052, U.S. Patent No. 3725067, JP-A-59-99437, JP-A-58-42045, JP-A-59-
No. 162548, JP-A-59-171956, JP-A-60-33552
The synthesis was carried out with reference to No. 60-43659 and JP-A-60-43659. The couplers of the present invention are usually 1 x 10 ^-3 mol to 1 mol, preferably 1 x 10 ^-2 mol per mol of silver halide.
It can be used in a range of mol to 8×10 ^-1 mol. The couplers of the present invention can also be used in combination with other types of magenta couplers. In the method for processing photographic materials 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 including bath processing, such as a spray method in which a processing chemical is atomized, a wet method in which contact is made with a carrier impregnated with a processing solution, and a developing method using a viscous processing solution, are also available. method can be used. In addition to the above, there are no particular limitations on the processing method for the photographic material of the present invention, and any processing method can be applied. For example, a typical example is
After color development, a bleach-fixing treatment is carried out, and if necessary, washing and/or stabilization treatment is carried out; after color development, bleaching and fixing are carried out separately, and if necessary, further washing and/or stabilization treatment is carried out; or Pre-hardening, neutralization, color development, stop fixing, washing with water, bleaching, fixing, washing with water, post-hardening, washing with water in that order, color development, washing with water, supplementary color development, stopping, bleaching, fixing, washing with water, stabilization No matter which method is used, the developed silver produced by color development is subjected to halogenation bleaching, and then color development is performed again to increase the amount of dye produced. good. 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, there are anti-stain agents, anti-sludge agents, preservatives, interlayer effect promoters, chelating agents, and the like. 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 aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid glycol ether diaminetetraacetic acidethylenediaminetetrapropionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acidpentasodium saltnitriloacetic acid sodium salt Bleaching solution contains 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. Then, as in the case of the bleach solution mentioned above, various other additives such as PH buffer, optical brightener, antifoaming agent, surfactant, preservative, chelating agent, stabilizer, organic solvent, etc. are added. ,
It may be included. The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned. Treatments other than color development of the silver halide color photographic light-sensitive material of the present invention, such as bleach-fixing (or bleaching,
From the viewpoint of rapid processing, it is preferable that the processing temperature of various processing steps such as fixing), washing with water, stabilization, etc., which are carried out as necessary, be carried out at 30° C. or higher. The silver halide color photographic material of the present invention is disclosed in JP-A-58-14834, JP-A-58-105145, and JP-A-58-58-1.
No. 134634 and No. 58-18631 and patent application No. 1983-
Stabilization treatment as an alternative to washing may be performed as shown in No. 2709 and No. 59-89288. A water-soluble or color-decolorizing dye (AI dye) can be added to the photographic constituent layer of the silver halide color photographic light-sensitive material of the present invention.
Dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful.
Examples of AI dyes that can be used include UK patent 584609
No. 1277429, JP-A-48-85130, No. 49-
No. 99620, No. 49-114420, No. 49-129537, No. 49-129537, No. 49-114420, No. 49-129537, No.
No. 52-108115, No. 59-25845, No. 59-111640,
No. 59-111641, US Patent No. 2274782, US Patent No. 2533472
No. 2956879, No. 3125448, No. 3148187,
No. 3177078, No. 3247127, No. 3260601, No. 3260601, No.
No. 3540887, No. 3575704, No. 3653905, No. 3540887, No. 3575704, No. 3653905, No.
Examples include those described in No. 3718472, No. 4071312, and No. 4070352. It is generally preferable to use these AI dyes in an amount of 2 x 10 ^-3 to 5 x 10 ^-1 mol, more preferably 1 x 10 ^-2 to 1 x 10 ^-1 mol, per mol of silver in the emulsion layer. The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [1.0.0] planes to [1.1.1] planes can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. In addition, tabular silver halide grains (JP-A-58-113934, patent application No. 59-170070)
) can also be used. Silver halide grains particularly preferably used in the present invention are substantially monodisperse, and may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method. Alternatively, for example, seed particles may be produced using an acidic method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. PH and pAg in the reaction vessel when growing silver halide grains
It is preferable to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains, for example, as described in JP-A-54-48521. Preferably, the silver halide grains according to the present invention are prepared as described above. A composition containing the silver halide grains is referred to herein as a silver halide emulsion. These silver halide emulsions contain activated gelatin;
Sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, polyamines, etc.; noble metal sensitizers such as gold sensitizers. Sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc. or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc. Specifically, ammonium chloroparadate, potassium chloroplatinate, and sodium chloroparadate (some of these substances act as sensitizers or fog suppressants depending on the amount) can be used alone or Chemical sensitization may be carried out by using an appropriate combination (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.). The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, the silver halide emulsion contains a nitrogen-containing heterocyclic ring having at least one hydroxytetradesign and a mercapto group. It may contain at least one kind of compound. The silver halide used in the present invention contains an appropriate sensitizing dye at a rate of 5 x 10 ^-8 per mole of silver halide in order to impart photosensitivity in the desired wavelength range.
Optical sensitization may be achieved by adding up to 3×10 ⁻³ mol.
Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following. That is, examples of sensitizing dyes used in blue-sensitive silver halide emulsions include West German Patent No. 929080, US Patent No. 2231658, US Patent No. 2493748, US Pat.
No. 2519001, No. 2912329, No. 3656959, No. 2519001, No. 2912329, No. 3656959, No.
No. 3672897, No. 3694217, No. 4025349, No. 3672897, No. 3694217, No. 4025349, No.
No. 4046572, British Patent No. 1242588, Special Publication No. 1977-
Examples include those described in No. 14030 and No. 52-24844. In addition, as sensitizing dyes used in green-sensitive silver halide emulsions, for example,
No. 1939201, No. 2072908, No. 2739149, No.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2945763, British Patent No. 505979, and the like. Furthermore, as sensitizing dyes used in red-sensitive silver halide emulsions, for example,
No. 2269234, No. 2270378, No. 2442710, No. 2269234, No. 2270378, No. 2442710, No.
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2454629, No. 2776280, and the like. Furthermore, US Patent No. 2213995, US Patent No. 2493748
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 2519001, West German Patent No. 929080, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions. These sensitizing dyes may be used alone or in combination. The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary. Representative examples of particularly preferred spectral sensitization methods include, for example, Japanese Patent Publications No. 43-4936, No. 43-22884, No. 45-4 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 18433, No. 47-37443, No. 48-28293, No. 49
-6209, 53-12375, JP-A-52-23931,
No. 52-51932, No. 54-80118, No. 58-153926
No. 59-116646, No. 59-116647, and the like. In addition, regarding the combination of carbocyanine having a benzimidazole nucleus and other cyanine or merocyanine, for example, Japanese Patent Publication No. 25831/1983;
No. 47-11114, No. 47-25379, No. 48-38406,
No. 48-38407, No. 54-34535, No. 55-1569,
JP-A-50-33220, JP-A No. 50-38526, JP-A No. 51-
No. 107127, No. 51-115820, No. 51-135528, No.
Examples include No. 52-104916 and No. 52-104917. Furthermore, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example,
No. 32753, No. 46-11627, JP-A No. 1483-1983, and Japanese Patent Publication No. 1483-1983 regarding merocyanine.
-38408, 48-41204, 50-40662, JP-A-56-25728, 58-10753, 58-91445
No. 59-116645, No. 50-33828, etc. In addition, regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publication No. 43
-4932, 43-4933, 45-26470, 46
-18107, JP-A No. 47-8741, JP-A-59-114533, etc. Furthermore, the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye is advantageous. It can be used for. In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone,
Dimethylformamide or Special Publication No. 50-40659
It is used by dissolving it in a hydrophilic organic solvent such as a fluorinated alcohol as described in the above. The additive may be added at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion. Although the green-sensitive silver halide emulsion layer according to the present invention contains the pyrazolotriazole-based magenta coupler of the present invention, a magenta coupler other than the present invention may also be used in combination with the green-sensitive silver halide emulsion layer. good. However, it is preferable that the amount of magenta couplers other than the present invention be less than 45 mol % based on the total amount of magenta couplers. Further, the blue-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer according to the present invention can each contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye. Yellow couplers that can be used in the present invention include open chain 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. 51-218427, No. 50-
No. 87650, No. 52-82424, No. 52-115219, No. 58
Examples include those described in No.-95346. Examples of magenta couplers that can be used in combination in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds outside the present invention. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers that can be used in combination include U.S. Patent No. 2600788;
No. 2983608, No. 3062653, No. 3127269, No. 3127269, No.
No. 3311476, No. 3419391, No. 3519429, No.
No. 3558319, No. 3582322, No. 3615506, No.
No. 3834908, No. 3891445, West German Patent No. 1810464,
West German patent application (OLS) No. 2408665, OLS No. 2417945,
No. 2418959, No. 2424467, Special Publication No. 40-6031,
JP-A No. 51-20826, No. 52-58922, No. 49-
No. 129538, No. 49-74027, No. 50-159336, No.
No. 52-42121, No. 49-74028, No. 50-60233,
No. 51-26541, No. 53-55122, Patent Application No. 1983-
Examples include those described in No. 110943. Furthermore, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. 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 Nos. 2,369,929, 2,434,272, and
No. 2474293, No. 2521908, No. 2895826, No.
No. 3034892, No. 3311476, No. 3458315, No.
No. 3476563, No. 3583971, No. 3591383, No. 3591383, No. 3583971, No. 3591383, No.
No. 3767411, No. 3772002, No. 3933494, No.
No. 4004929, West German Patent Application (OLS) No. 2414830,
JP-A No. 2454329, JP-A-48-59838, JP-A No. 51-26034
No. 48-5055, No. 51-146827, No. 52-
Examples include those described in No. 69624, No. 52-90932, No. 58-95346, and Japanese Patent Publication No. 49-11572. 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 pyrazolotriazole magenta coupler of the present invention into the silver halide emulsion of the present invention, if the pyrazolotriazole magenta coupler of the present invention is alkali-soluble, it is added as an alkaline solution. It's okay,
If it is oil-soluble, e.g.
2322027, 2801170, 2801171, 2272191, and 2304940, the pyrazolotriazole magenta coupler of the present invention is added to a high boiling point solvent as necessary. It is preferable to dissolve it in combination with a low boiling point solvent, 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. It is also possible to use a mixture of two or more types of pyrazolotriazole magenta couplers of the present invention. Further, to describe in detail the method of adding the pyrazolotriazole magenta coupler of the present invention which is preferred in the present invention, one or more types of the pyrazolotriazole magenta coupler of the present invention may be added as necessary to other couplers, Hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc., as well as organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, tri-
Cresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n-butyl sebacate, tri-n-hexyl phosphate, N,N-di-ethyl-caprylamidobutyl, N,N-diethyl lauramide , n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3-pentadecyl phenyl ethyl ether, 2,5-di-sec-amyl phenyl butyl ether, monophenyl-di-o-chlorophenyl phosph ate or high boiling point solvents such as fluoroparaffin, and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol,
Dissolved in low boiling point solvents such as diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexane tetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, and anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids. and/or mixed with an aqueous solution containing a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate and/or a hydrophilic binder such as gelatin, and mixed with a high-speed rotary mixer, colloid mill, ultrasonic dispersion device, etc. It is emulsified and dispersed and added to the silver halide emulsion. 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 JP-A-49-74538 and JP-A-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, such as those published in 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 the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Examples include cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide. Examples of the support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, such as a glass plate, and cellulose acetate. , a polyester film such as cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, etc. Other usual transparent supports may also be used. These supports are appropriately selected depending on the intended use of the photosensitive material. Various coating methods such as dip coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and other photographic constituent layers used in the present invention. Further, simultaneous coating of two or more layers by the methods described in US Pat. No. 2,761,791 and US Pat. No. 2,941,898 can also be used. In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photosensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer from the support side. 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 light-sensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and various layers such as a filter layer, anti-curl layer, protective layer, anti-halation layer, etc. may also be provided as constituent layers. They can be used in appropriate combinations. 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 using a color developing solution at a low replenishment amount, the bromide ion concentration does not change and constant appropriate photographic performance can be maintained over a long period of time. To provide a quick and stable processing method for silver halide color photographic materials in which colored dyes and uncolored areas do not fade or change color even after long-term storage, and there is little magenta fog when heavy metal ions are mixed in. can be provided. [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. Example 1 On a paper support laminated with polyethylene,
The following layers were sequentially coated from the support side to prepare silver halide color photographic material samples Nos. 1 to 25. Layer…1.1g/ ^m2 gelatin, silver amount 0.30g/ ^m2
Blue-sensitive silver halide gelatin emulsion (silver halide composition and average grain size are shown in Table 1).
Shown below. ), 0.82 g/m ^{2 of} yellow coupler (Y-
A blue-sensitive silver halide emulsion layer containing 1). Layer 2: Intermediate layer consisting of 0.72 g/m ² of gelatin and 15 mg/m ² of anti-irradiation dye. Layer 3…1.25g/ ^m2 gelatin, silver amount 0.29g/m2
m ² of green-sensitive silver halide gelatin emulsion (silver halide composition and average grain size are shown in Table 1), 0.30 g/
A green-sensitive silver halide emulsion layer containing 0.60/ ^{m 2 of} magenta coupler Exemplary Compound No. 18 dissolved in m 2 of dioctyl phthalate. Layer 4: Intermediate layer consisting of 1.2 g/m ² of gelatin. Layer 5...1.3g/ ^m2 gelatin, silver amount 0.26g/m2
m ² red-sensitive silver halide gelatin emulsion (silver halide composition and average grain size are shown in Table 1), 0.21 g/
0.46g/ ^m2 dissolved in ^m2 of dioctyl phthalate
A red-sensitive silver halide emulsion layer containing a cyan coupler (C-1). Layer 6...Protective layer containing 0.49 g/m ² of gelatin. The silver halide in each of the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer was one whose color had been increased by a general sensitizing dye. In addition, as a hardening agent, 2,4-dichloro-6-
layer 2 of sodium hydroxy-S-triazine;
0.02g per 1g of gelatin in 4 and 6 respectively
After drying, the gelatin film swelling rate T1/2 was measured at 30° C. using the following color developing solution and found to be about 8 seconds. The measurement was carried out using a Lebenzon type swelling meter. Each of the photosensitive material samples Nos. 1 to 25 shown in Table 1 was exposed through an optical wedge and then processed in the following steps. Processing steps (38°C) Color development 120 seconds Bleach-fixing 60 seconds Washing with water 60 seconds Drying 60-80°C 120 seconds The composition of each processing solution 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 Nitrilotriacetic acid 2.0g Color developing agent (as shown in Table 1) 0.023mol Magnesium chloride 0.3g Carbonic acid Potassium 32g Kaycoll-PK-Conc (fluorescent brightener, manufactured by Shin Nisso Kako Co., Ltd.) 2ml Add pure water to 1 and make 20% potassium hydroxide or
Adjust the pH to 10.1 with 10% dilute sulfuric acid. [Bleach-fix solution] Pure water 550ml Iron ethylenediaminetetraacetate () Ammonium salt 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 is 0.6.
The same sample as above using a color developer with the only difference being that g/ is 1.5 g/ and 3.5 g/
Each of Nos. 1 to 25 was developed. Sensitometry was performed on each of the obtained samples by a conventional method. Potassium bromide concentration 0.6g/
The density of each sample after exposure when the density is around 1.0 is
Table 1 shows the concentration changes when the potassium bromide concentration was varied. As for the color density ratio, only the cyan density is shown in Table 1.

【table】

[Table] As is clear from the results in Table 1, Samples No. 1 to No. 1 in which the silver halide was not substantially chlorobrominated.
Compared to sample No. 12, sample No. 12 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 even when the amount is changed to 3.5 g/min, there is not much change in the color density, indicating that the processing stability is high. In contrast, the conventionally known color developing agent CD-3
In the case of CD-6, it can be seen that regardless of the composition of silver halide, in all cases there is a drawback that the color density decreases as the bromide ion concentration in the color developer increases. . Note that Table 1 shows that as the bromide ion concentration increased, the amount of replenishment was reduced, indicating that the treatment of the present invention can significantly reduce the amount of replenishment. Example 2 Silver halide photographic material sample No. 21 of Example 1
Using the same processing solution as in Example 1, the film was exposed and developed in the same manner as in Example 1. Color developing solutions were prepared by changing the color developing agent as shown in Table 2 and used for processing.
The color development time was varied as shown in Table 2. The treatment temperature was 38°C. The obtained sample was stored under irradiation with a xenon lamp, and changes in cyan concentration were measured. In other words, when the initial sample density of 1.0 when using CD-3 as the color developing agent deteriorates by about 0.3 at each processing time, the decrease in concentration in the same concentration range of the sample treated with another color developer is measured. It is shown in Table 2. At this time, the yellow stain density of the unexposed area of the same sample was measured and similarly shown in Table 2.

[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 a large difference in the fading rate no matter how many seconds the color development time is. It is not allowed. Especially CD-3
It can be seen that the color fading is greater in the case of CD-6 than in the case of CD-6. This also applies to the yellow stain density (Dmin) in the unexposed area. On the other hand, the color developing agent exemplified compound (1) of the present invention or
In the case of (2), if the color development processing time is 180 seconds or more, the color will fade significantly and the storage stability will be extremely low. This also applies to the yellow stain density (Dmin) in the unexposed area. However, it can be seen that when the color development time is 150 seconds or less, the storage stability is rapidly improved, resulting in more favorable results than when using CD-3. This is surprising considering that it has traditionally been said that the structure of coloring dyes is closely related to their stability, and it is predicted that the residual amount of color developing agent in the film may also be closely related. Ru. Example 3 Using each of the silver halides of Sample No. 3 and No. 21 of Example 1, the amount of silver halide was determined so that the amount of silver coated in the blue, green, and red sensitive emulsion layers was the same as in Example 1. Samples were prepared with various amounts of hardening agent added. After drying, the membrane swelling rate T1/2 of the sample was measured using the above-mentioned color developing solution (measurement processing temperature: 30° C.) using a Lebenzon type swelling meter. Membrane swelling rate T1/2 is 2 seconds, 5 seconds, 10 seconds, 15 seconds, 30 seconds, 40 seconds,
Samples with 60 seconds, 90 seconds, and 120 seconds were selected and used in the experiment. 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. The maximum density of cyan when color development is performed at 38℃ for 10 minutes is 100, and the processing time required to reach the maximum density of 80 is shown in Table 3.
It was shown to. This result shows the rapidity of the development completion point.

[Table] As is clear from the results in Table 3, when the silver halide is silver chlorobromide, the color developing agent is according to the present invention, and the film swelling rate T1/2 is extremely fast when it is 30 seconds or less. The development completion (arrival) time is shown, and it can be seen that rapid development processing is possible. On the other hand, even if the color developing agent of the present invention is used, if the membrane swelling rate T1/2 is 40 seconds or more, the time to complete development (attainment) will suddenly become longer; Even if the membrane swelling rate T1/2 was very low, a fast development completion time could not be obtained. On the other hand, when the silver halide is substantially silver iodobromide, even if the color developing agent is of the present invention, the development completion time is fast regardless of the film swelling rate T1/2. It turns out that you can't get it. Example 4 Using the silver halide photographic materials of Samples No. 3 and No. 21 of Example 1, the blue, green, and red sensitive emulsion layers were made to have the same amount of silver, and the total amount of silver was 0.4 g/ ^m2 ,
0.75g/m ² , 1.0g/m ² , 2g/m ² , 3g/m ² ,
Samples were prepared by coating at 5 g/m ² and 7 g/m ² . The membrane swelling rate T1/2 (measurement processing temperature: 30°C) of each sample was 8 seconds. The coupler was prepared using the amount of Example 1 at 1.0 g/m ² and the other ratios were varied depending on the silver amount ratio. The same processing solution as in Examples 1, 2, and 3 was used except that the color developing agent was changed. Bromide ion concentration is potassium bromide 1.5g/
And so. The maximum density when the color developer was used for color development at 38° C. for 10 minutes was set as 100, and the processing time required to reach the maximum density of 80 was measured and shown in Table 4. As in Example 3, the development completion time is shown.

【table】

[Table] As is clear from the results in Table 4, even with the process of the present invention, as the total amount of silver increases, the development completion time tends to increase rapidly, but development is completed significantly compared to the comparative process. I understand that time is short. Example 5 A color paper sample was prepared in the same manner as in Example 1 except that the magenta coupler of the color paper used in Example 1 was changed to the coupler shown in Table 5 below. Furthermore, this sample was developed in the same process as in Example 1, and then a bleach-fix solution was added to the color developer to give an iron ion concentration of 3 ppm, and the sample was left in an open beaker for 5 days. Thereafter, a similar development process was carried out using this color developing solution, and the difference in magenta stain density between the unexposed developed color paper before and after storage was measured using a densitometer. The above results are shown in Table 5.

【table】

[Table] As is clear from the results in Table 5, when using the coupler represented by the general formula [] of the present invention, heavy metal ion The developing agent of the present invention (N-hydroxyalkyl-substituted-p
-phenylenediamine derivatives), the generation of magenta stain is particularly suppressed, which is very good. This means that even when heavy metal ions are mixed into the color developer (e.g., iron ions in the bleach-fix solution or from water when the color developer is dissolved), a visually noticeable magenta stain can occur on the white background. This means that stable processing performance can be obtained. Example 6 Photosensitive material (color paper) used in Example 1
The magenta coupler contained therein was varied as shown in Table 6 below, and the film swelling rate was similarly varied as shown in Table 6 by varying the amount of hardener added. Furthermore, experiments were conducted by changing the color developing agent, processing time, and processing temperature in the color developer solution as shown in Table 6. The samples were stored under xenon lamp irradiation as in Example 2, and the cyan dye concentration and yellow stain were changed. The change in was measured. Furthermore, the reflection density of the highest yellow dye density area (Dmax) and the unexposed area (Dmin) immediately after the development process was measured. The results are summarized in Table 6.

【table】

[Table] According to Table 6 above, the processing method of the present invention has good yellow stain and cyan dye fading after storage with light irradiation, and provides sufficient yellow dye density without yellow stain immediately after development. It turns out that there is something.

[Brief explanation of drawings]

FIG. 1 is a graph showing the membrane swelling rate T1/2 of the binder.

Claims (1)

[Scope of Claims] 1. In a method for developing a silver halide color photographic light-sensitive material, the silver halide emulsion in at least one light-sensitive emulsion layer is substantially a silver chlorobromide emulsion, and the binder film swells. A silver halide color photographic light-sensitive material having a speed T1/2 of 30 seconds or less and containing a magenta coupler represented by the following general formula [] in the green-sensitive emulsion layer is prepared using N-hydroxyalkyl-substituted-p-phenylenediamine. 1. A method for processing a silver halide color photographic light-sensitive material, which comprises developing at a temperature of 30° C. or higher and 150 seconds or less using a color developing solution containing a derivative. General formula [] In the formula, Z represents an atomic group necessary to form a five-membered ring consisting of a carbon atom or a nitrogen atom, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. 2. The halogenated compound according to claim 1, wherein the silver halide emulsion of at least one photosensitive emulsion layer is a silver chlorobromide emulsion having a silver bromide content of 90 mol% or less. Processing method for silver color photographic materials. 3. The method for processing a silver halide color photographic material according to claim 1 or 2, wherein the total coating amount of silver in the silver halide color photographic material is 1 g/m ² or less. 4. The method for processing a silver halide color photographic material according to any one of claims 1 to 3, wherein the color developing solution contains at least 5 x 10 ^-3 moles of bromide. 5. A method for processing a silver halide color photographic light-sensitive material according to claim 4, which comprises processing with a color developing solution containing 1×10 ^-2 mol or more of bromide. 6. The method for processing a silver halide color photographic light-sensitive material according to claim 4, characterized in that the material is processed with a color developing solution containing 1.5×10 ^-2 mol or more of bromide. 7. The method for processing a silver halide color photographic material according to any one of claims 1 to 6, characterized in that the film swelling rate T1/2 of the binder is 20 seconds or less. 8. The method for processing a silver halide color photographic light-sensitive material according to claim 3, characterized in that the total amount of coated silver is 0.8 g/m ² or less. 9 N-Hydroxyalkyl-substituted-p-phenylenediamine derivative is 3-methyl-4-amino-N
9. The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 8, characterized in that the salt is -ethyl-N-β-hydroxyethylaniline salt. 10. The silver halide color photographic material according to any one of claims 1 to 9, characterized in that the color photographic material is processed with a replenishment amount of 250 ml/m ² or less during continuous processing. processing method. 11. The method for processing a silver halide color photographic material according to claim 10, wherein the color photographic material is processed at a replenishment amount of 200 ml/m ² or less during continuous processing.