JPS6290656A - Treatment of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To execute stable color development by developing a silver halide color photographic material contg. silver chlorobromide emulsion and Fisher dispersed coupler with N-hydroxyalkyl substituted-p-phenylenediamine compd. CONSTITUTION:A silver halide photographic sensitive material contg. silver chlorobromide emulsion of 5-60mol% silver bromide content and Fisher dispersed coupler in at least one layer of the silver halide emulsion is used. The material is developed with a developer contg. an N-hydroxyalkyl-substituted-p- phenylenediamine deriv. (expressed by the formula, wherein R1 is H, alkyl, alkoxy; A is OH, alkyl having an OH group; HX is HCl, etc.). The color development is executed at >=30 deg.C for <=150sec. Thus, the development is executed appropriately and for a long period without being influenced by the bromide ion concn. even if the color development is executed using a small amt. of supplemental developer.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a color development processing method for silver halide color photographic light-sensitive materials (hereinafter referred to as photographic elements). This invention relates to a novel processing method that has less dependence on bromide ion concentration fluctuations and dependence on processing temperature and pH value of a color developing solution, does not impair rapidity, and provides dye images with excellent chromaticity and long shelf life. In particular, it relates to a processing method that requires a small amount of replenishment and has high processing stability.

[Prior Art] Processing of photographic elements basically consists of two steps: color development and desilvering, with desilvering consisting of a bleaching and fixing step or a bleach-fixing step. In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps.

In color development, 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 the reduction of silver halide are eluted into the developer and accumulate. Additionally, components contained in the photographic element, such as inhibitors, are also eluted and accumulated in the color developer.

In the desilvering step, the silver produced by development is bleached by an oxidizing agent, and then all silver salts are removed from the photographic element as soluble silver salts by 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.

In color developing solutions, development inhibiting substances accumulate as the photographic element is developed as described above, but on the other hand, the color developing agent and benzyl alcohol are consumed or accumulated in the photographic element and taken out, and the concentration of these components decreases. Therefore, in a developing method in which a large amount of photographic elements are continuously processed using an automatic processor, etc., the components of the color developing solution are kept within a certain concentration range in order to avoid changes in the development finish characteristics due to changes in component concentration. A means is needed to maintain it. As such a method, a method of replenishing a replenisher is usually used to supplement the missing components and dilute the unnecessary increased components.

The replenishment of this replenisher inevitably results in large amounts of overflow, which are discarded, making this method a major economic and pollution problem. Therefore, in recent years, in order to reduce the amount of overflow liquid, a so-called concentrated low replenishment 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 be subject to large changes due to even a slight error in the amount of replenishment.
It is also more susceptible to the effects of concentration due to evaporation. 1 Usually, the concentration of the fatigue accumulation mentioned above increases. 0 For example, when the halogen ion concentration increases, the development response is suppressed and the leg of the characteristic curve is further suppressed. This creates a problem of high contrast due to the 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 evaporation and regeneration operations (fluctuations in bromide ion concentration), and differences in throughput, especially during weeks with high orders. The difference between the beginning and weekends when the number of orders decreases, and the high season and the off-season is a maximum of 1:5 difference, and the composition of the processing solution is also affected by evaporation and differences in the amount of replenisher. There are disadvantages that make them different.

Therefore, low-replenishment processing and regeneration methods require efforts to quantitatively analyze the components and make the composition constant each time they are regenerated. Therefore, it is difficult to implement these regeneration processing and low-replenishment processing in photo labs, mini-labs, etc. without special skills. There are many things like that.

These gaps are mainly due to changes in bromide ions, which are development inhibitors.1 For example, reducing the amount of bromide ions that accumulate in photographic elements can reduce the amount of bromide ions that accumulate, or reduce the amount of bromide ions that accumulate due to evaporation. It has also been proposed to reduce fluctuations in the concentration of bromide ions due to errors in the amount of replenishment (see Japanese Patent Application Nos. 59-173189 and 59-205540, etc.).

It is also presumed that these problems can be solved by improving developability, for example by reducing the average grain size of silver halide in the photographic element or by lowering the amount of coated silver. certain 3-methyl-4-
In a color developer using amino-N-ethylroot β-methanesulfonamide ethylaniline, even though the developability was improved, the processing stability did not improve as much as expected, and the bromide ion concentration in the developer did not improve as much as expected. I am affected by it.

However, it is an important issue to improve processing stability while shortening processing time.

Conventionally, in color paper processing consisting essentially of silver chlorobromide emulsion, color development was performed at 33°C for 3 minutes and 30 seconds - bleach-fixing 33
°C, 1 minute and 30 seconds - 3 minutes of water washing (or 3 minutes of stabilization) - drying. The total processing time is generally about 8 minutes, but the strong demand of the times is the above-mentioned low replenishment from an economic point of view, but short processing times are also strongly requested from the viewpoint 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 agents, which have traditionally been used as crude drugs most suitable for developing silver chlorobromide emulsions, penetrate slowly into photographic elements, and various penetrants have been investigated to speed up the penetration of color developing agents into photographic elements. For example, a method of adding benzyl alcohol to a color developer to accelerate color development is widely used. However, with this method, 33
6. Method of increasing the p)I of the color developing solution, which had the drawback of not only not developing sufficient color unless it was processed for 3 minutes or more at °C, but also being easily affected by the subtle bromide ion concentration. It is also known that when the pH reaches 10.5 or higher,
The problem is that the oxidation of the color developing agent becomes extremely rapid, and because there is no suitable buffer solution, it becomes susceptible to pH changes, making it impossible to obtain stable photographic properties, and increasing the dependence on processing time. There was a point.

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 photographic element in advance. For example, a method is known in which a color developing agent is incorporated in the form of a metal salt. (U.S. Pat. No. 3,719,492), but it is known that this method has disadvantages in that the photographic element has poor shelf life and is prone to fogging before use and also being prone to fogging during color development.

Furthermore, in order to inactivate the amine part of the color developing agent,
For example, a method of incorporating a color developing agent into ship salt (U.S. Pat. No. 3,342,559, Re5earch
Disclosure, 1978 No. 151
59) However, it is known that these methods have the disadvantage that color development cannot be started 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 is known.

Yet again. It is known that 3-pyrazolidones are added to a black and white developer solution containing a developer such as hydroquinone to accelerate development (for example, F, A).

+1ason, Photographic Pro
ceSsing Chemistry, pp. 103-107, Focal Press, 1988), the fact that this compound is incorporated into photographic elements is covered by British Patent No. 787.7.
However, in the technology described in the above patent specification, the silver halide photosensitive material is incorporated into a black and white silver halide photographic light-sensitive material or a reversal photographic element, and its purpose is to promote only black and white development. It is also published in Japanese Patent Application Laid-Open No. 53-5242.
No. 2 contains 3-pyrazolidones in a photographic element for the purpose of preventing a decrease in sensitivity in an unexposed state of a photographic element containing a 2-equivalent magenta coupler having 7 oxy-type organic sprifio groups at the active site. However, these techniques are not suitable as a rapid method of stabilizing one-color development processing with low replenishment processing.

Further, as a conventionally known method of accelerating color development using an accelerator, US Pat. No. 2,950,970;
2,515,147, 2.498.903, 4.03B, 075, 4,119,482, British Patent 1,430,998, 1,455,413,
JP 53-15831, JP 55-62450, JP 55-62451, JP 55-62452, JP 55-
No. 62453, Special Publication No. 51-12322, No. 55-4
Compounds described in No. 9728 and the like were investigated.

Most of the compounds have an insufficient accelerating effect, and compounds that exhibit a high accelerating effect not only have the disadvantage of forming fog, but are not suitable as a method for improving processing stability.

Furthermore, the provision of a substantially non-photosensitive silver halide emulsion layer in a photographic element to facilitate development was disclosed in Japanese Patent Application Laid-Open No.
No. 23225, No. 56-14236, British Patent 1, 3
No. 78,577, OK, No. 32,822,922, etc., and its function is to adsorb development inhibiting substances such as unnecessary halogens released during development and unnecessary leaving groups of DIR couplers. It does not actively promote development, and its development promotion effect is only small.Although it is effective against fluctuations in iodide ion concentration, it has no processing stabilizing effect on fluctuations in bromide ion concentration. was not obtained.

On the other hand, it is said that the speed of color development varies depending on the type of paraphenylenediamine rust conductor used and depends on the redox potential. Among these color developing agents, N
, N-diethyl-p-phenylenediamine sulfate and 3-
N-alkyl-substituted color developing agents with low water solubility, such as methyl-4-amino-N,N-diethylaniline hydrochloride, have high development activity and can be speeded up, but the coloring dye tends to fade after processing. is known to be low and undesirable. On the other hand, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline is said to be preferable because of its high developing activity (see U.S. Pat. No. 3,858.950, U.S. Pat. No. 3,858,525, etc.). -P-) Although luenesulfonate does provide rapidity, it does not provide stability in bromide ion concentration and causes significant yellow stain in the unexposed areas of photographic elements after processing, especially when processed for a short period of time. It has been found that this method cannot be used in rapid processing because it has the disadvantage that a single color developing agent remains behind and causes rough staining.

On the other hand, 3-methyl-4-aminotoethyl)re β-methanesulfonamide ethylaniline sesquisulfate monohydrote and 3-methyl- 4-Amino-N-β-hydroxyethylaniline sulfate, etc. are published in Photographic Φ Science and Engineering Vol. 1.8. No, 3.5~6
Moon, 1964, P, 125-137,
It was said that there was not much difference in the half-wave potential indicating the redox potential, and that both had weak development activity. Therefore, it was said that the development activity for silver chlorobromide emulsions was high and the storage stability of dye images was excellent. It is said that there is almost no developing agent, and 3-methyl-4-amino-N-ethyl-X-β-methanesulfonamidoethylaniline sulfate was generally used together with benzyl alcohol.

However, in this case, as mentioned above, it is easily affected by changes in bromide ion concentration, and another problem with concentrated low replenishment processing in which the amount of replenisher is reduced is that the contamination and accumulation of other processing solution components increases. be.

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. , other processing liquids may be mixed in due to splashes from adjacent processing liquids in the processing machine, transport leader,
This is caused by so-called back contamination, in which components of the processing solution immediately after development are brought into the color developing solution by a belt or a hanger for suspending the film. 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. Particularly by promoting the shoulders of the photographic characteristic curve, a markedly high contrast is thereby 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 is greatly accelerated at temperatures above 30°C. 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 in order to improve economy and environmental pollution, rapid processing is possible, photographic performance is maintained constant, and active ingredients do not decompose even if the processing solution is used for a long time. At present, there is a strong desire for a color developing solution that can be stably processed without causing any change in photographic processing performance.

The first object of the present invention is to maintain constant appropriate photographic performance over a long period of time without any change in bromide ion concentration even when processed with a color developing solution at a low replenishment amount. To provide a rapid and stable method for processing photographic elements 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 first objective, the present inventors have succeeded in discovering a unique color developing agent that is almost unaffected by the bromide ion concentration when developing a specific silver halide, and has obtained an advantageous result. Although the storage stability of the color dyes developed in the 1990s was greatly improved, the concentration of the color dyes was easily affected by the processing temperature fluctuations of the color developer and the p)I fluctuations, and the photographs of each light-sensitive silver halide emulsion layer When we encountered the problem of inconsistent performance, we further investigated ways to solve this problem.

[Means for Solving the Problem] As a result, in a method for processing a photographic element having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, The silver halide emulsions of at least the green-sensitive and red-sensitive silver halide emulsion layers are substantially silver chlorobromide emulsions having a silver bromide content of 5 to BO mol %, and the silver halide emulsions of at least the light-sensitive silver halide emulsion layers are The above objects can be achieved by processing a photographic element, one layer of which contains a Fischer-dispersed coupler, with a color developer containing a tohydroxyalkyl-substituted-p-phenylenediamine derivative for at least 30° C. and no more than 150 seconds. I found out what I can do.

Hereinafter, the progress that led to the present invention will be explained.

The inventor has discovered that when developing photographic elements using certain silver halide, i.e. silver chlorobromide based emulsions, the color developing agent is N-
It has been surprisingly discovered that only when a hydroxyalkyl-substituted p-phenylenediamine derivative is used, the dye density obtained hardly decreases even if the bromide ion concentration increases. The aforementioned characteristics of this color developing agent cannot be obtained in photographic elements using substantially silver iodobromide emulsions containing more than 0.5 mole % of silver iodide; This is unexpected since silver bromide emulsions have been used exclusively for developing emulsions, and development speeds are slow even when the bromide ion concentration is significantly increased when developing photographic elements using substantially silver chlorobromide emulsions. The fact that there is no delay is unexpected, and cannot be understood from the redox potential or half-wave potential of common color developing agents, and it is likely that a perfect balance between development speed and coupling speed is maintained. This cannot happen unless
It was surprising.

However, the inventor encountered the following problem. When an N-hydroxyalkyl-substituted-p-7-nylene diamine color developing agent is used, it is rapid and unaffected by changes in bromide ion concentration, and can be developed especially under high bromide ion concentrations, so it can be used in continuous processing. Although it has the great advantage of being able to significantly reduce the amount of replenishment and extremely high processing stability, it has been found that it has the disadvantage that the storage stability of the resulting color pigment, especially the ancestral color properties, is reduced. The storage stability of zero-dye images is critical and has become a major obstacle, especially in the case of color paper (prints).

The present inventor further worked hard to solve this problem, and as a result 1
It was found that this problem is not due to the low storage stability of the dye itself, but because the color developing agent tends to remain in the photographic element, and that this problem can be solved by shortening the color development time. However, shortening the color development time cannot be achieved unless the processability of the photographic element is sufficiently improved - it cannot generally be shortened, but it can be achieved by reducing replenishment and processing stability without compromising the storage stability of the dye image. It has been found that in order to achieve this property, it is necessary to use the color developing solution of the present invention and process at a temperature of 30° C. or higher and within 150 seconds.

In this case, if conventional photographic elements are used as they are, there will be a problem that developing time will be insufficient and sufficient photographic images will not be obtained. Therefore, the inventors of the present invention have conducted further studies and developed a method using the color developing agent of the present invention. In order to carry out low replenishment processing without being affected by an increase in ion concentration, the silver halide emulsions of at least the green-sensitive and red-sensitive silver halide emulsion layers have a substantial salt content of 5 to 60 mol % silver bromide. The development rate is improved by processing a photographic element, which is a silver bromide emulsion, with a developer containing an N-hydrodialkyl-substituted-P-phenylenediamine derivative, and the photographic element is processed in a range of 30" to 150 seconds. The first object of the present invention has been successfully achieved without impairing the stability of the dye image by carrying out rapid color development.

However, although this technique is not affected by increases in the bromide ion concentration of one color developing solution, it is affected by pH fluctuations and temperature fluctuations of the color developing solution, and the coloring dye concentration of each light-sensitive silver halide emulsion layer is affected. It was found that certain photographic performance could not be obtained with respect to the following methods.

In order to solve this problem, research by the present inventors has revealed that, quite surprisingly, the above problem can be solved by using a Fischer dispersion coupler in at least one of the light-sensitive silver halide emulsion layers. The present invention has now been completed. Furthermore, it has been found that the bromide ion concentration dependence can be further improved according to the present invention.

In this specification, "substantially silver chlorobromide emulsion" to "
"Substantially silver chlorobromide emulsion" means that it may contain a trace amount of silver iodide in addition to silver chlorobromide, for example, 0.3 mol % or less, more preferably 0.1 mol % or less iodide. This means that it may contain silver. 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 light-sensitive emulsion layers of photographic elements processed according to the present invention are comprised of two
The silver bromide content of at least the green-sensitive and red-sensitive silver halide emulsion layers is substantially comprised of a silver chlorobromide emulsion (hereinafter referred to as the silver chlorobromide emulsion of the present invention) with a silver bromide content of 5 to 60 mol %.

Each of the blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and red-sensitive silver halide emulsion layer in the present invention may be composed of two or more layers. In the present invention, the silver bromide content refers to the total silver halide content contained in each of the total green-sensitive silver halide emulsion layer, the total blue-sensitive silver halide emulsion layer, and the total blue-sensitive silver halide emulsion layer. This refers to the total silver bromide content in each layer. When the silver bromide content exceeds 60 mol %, processing stability deteriorates. In addition, from the viewpoint of processing stability, it is preferable that the silver bromide content does not fall below 5 mol%.
In the wood invention, the preferred silver bromide content of at least one photosensitive emulsion layer (preferably all photosensitive emulsion layers) is 20 to 55 mol%, more preferably 30 to 50 mol%.
It is.

The composition of the silver halide contained in the photosensitive emulsion layer not based on the silver chlorobromide emulsion of the present invention is not particularly limited, and any of silver bromide, silver chlorobromide, and silver chloroiodobromide may be used. good.

The average grain size of the silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention is not limited, but
Preferably it is 0.20 to 0.55 gm, more preferably 0.25 to 0.50 gm. In terms of processing stability, an average particle size of 0.55 LLm or less is preferable, while an average particle size of 0.20 LLm or less is preferable in terms of sensitivity and prevention of magenta color turbidity.
The above is good.

The average grain size of the silver halide contained in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is also not particularly limited, but is preferably from 0.1 to 2 p.l.

More preferably 0.2 to Igm, particularly preferably 0.
25-0.8 pot 1.

The average grain size of silver halide can be measured by various methods commonly used in the art for the above purpose, and the average grain size of silver halide is defined as cubic silver halide grains. In the case of , it is the length of its -side, and in the case of a shape other than a cube, it is the length of one side when converted to a cube having the same volume.

Coating frft! in photographic elements of the invention! ! The smaller the amount, the more preferable it is because there is no delay in development due to the increase in bromide and sufficient dye formation can be achieved in a short time.
g/m2, especially 0.4 to 0.8 g/m'', the maximum effect is obtained.

Although the silver halide used in Wood's photographic elements may be polydisperse emulsions with average grain sizes distributed over a wide range, substantially monodisperse emulsions are preferred.

The above-mentioned substantially monodisperse silver halide grains are those in which most of the silver halide grains appear to have the same shape and uniform grain size when the emulsion is observed using an electron microscope.
And it has a particle size distribution as defined by the following formula. That is, when the standard deviation S of the particle size distribution is divided by the average particle size Te, the value is 0.20 or less, preferably 0.15 or less.

-≦0.20 The particle size here has the same meaning as the particle size described above regarding the average particle size.

The color development process in the present invention 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 30 seconds or less, and at 30°C or higher. When the treatment is carried out for 150 seconds or more, the storage stability of the dye deteriorates. In particular, processing time is more important than processing temperature, and if it exceeds 150 seconds, the ancestral color of the cyan dye will increase significantly, which is undesirable.The processing temperature should be raised to complete development in a short time rather than to maintain the storage stability of the dye. The higher the temperature is, the higher the temperature is, the higher the temperature is, the higher the temperature is, the shorter the treatment time, the more preferable it is, the higher the temperature is, the higher the temperature is, the higher the temperature is, the higher the temperature is, the higher the temperature is, the shorter the treatment time, the more preferable it is, the higher the temperature is, the higher the temperature is, the higher the temperature is, the higher the temperature is, the shorter the treatment time is, the more preferable it is, the higher the temperature is, the higher the temperature is, the shorter the treatment time, the more preferable it is, the higher the temperature is, the higher the temperature is, the higher the temperature is, the shorter the treatment time is, the more preferable it is, the higher the temperature is, the higher the temperature is, the shorter the treatment time is, the more preferable it is, the higher the temperature is, the shorter the treatment time is, the more preferably it is, the higher the temperature is, the higher the temperature is, the shorter the time
Most preferably, the treatment is carried out at a temperature of 35°C or higher and 43°C or lower.

The pH of the color developing solution is usually preferably 7 or more, more preferably in the range of 9 to 13.

An effective developing agent in the present invention is a quaternary ammonium salt of a tohydroxyalkyl-substituted-p-7 enylenediamine compound, particularly one that can be represented by the following general formula.

In the formula, R1 is a hydrogen atom, an alkyl group having 1 to 4 (11 carbon atoms), or an alkoxy group having 1 to 4 carbon atoms, Rz is a hydrogen atom, or 1 to 4
R:I is an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, and A has at least one hydroxyl group and is not branched. R4, R5, and Rs are each a hydrogen atom, a hydroxyl group, or 1 to 3 carbon atoms that may have a hydroxyl group, and are more preferably *CHz fC7C) [z $Rs Rs. represents an alkyl group that satisfies the following, and at least one of R4, R5, and R6 is a hydroxyl group or an alkyl group having a hydroxyl group. nt, R2 and R3 are each 0, 1.2 or 3, and HX represents hydrochloric acid, sulfuric acid, P-)luenesulfonic acid, nitric acid or cationic acid.

Such p-phenylenediamine color developing agents are unstable in their free amines and are commonly used as salts (most commonly those specified by the formula above); a typical example is as ζ-amino-3-methyl-
Examples include N-ethyl-N-(β-hydroxyethyl)-aniline salt and 4-aminoethyl-N-(β-hydroxyethyl)-aniline salt.

Preferably, in the present invention, 4-amino-3-methyltoethyl-N-(β-hydroxyethyl)-aniline sulfate hydrate [which is commercially available under the name CD-4 and is used in most In color photography methods (for example, Eastman Kodak 041 method, Konishiroku Photo Industries CN)
(used for developing color negative films such as the K-4 system) has been 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.

Margin below [Exemplary compounds] H2 -W.

NH2 N.H.

N.H.

Particularly preferred are hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid salts of the compounds (1) to (8) above.

Among these exemplified compounds, No., (1), (2),
(8).

(7) and (8) are preferably used, especially No., (1
), (2) and (6) are preferably used. moreover,
Toriwa (particularly No. (1)) 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 in the range of 1 g to 100 g per processing solution. is preferable, more preferably 3 g to 30
It is used in the range of g.

These N-hydroxyalkyl-substituted-p-phenylenediamine derivatives of the present invention are described in the Journal of American
Chemical Engineering 73@.

It can be easily synthesized by the method described on page 3100 (1951).

It goes without saying that other color developing agents can be used in combination with the N-hydroxyalkyl-substituted p-phenylenediamine derivative developing agent in the color developing solution according to the present invention. As the color developing agent which may be used in combination, p-phenylenediamine type ones are typical, and primary ones are mentioned as preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methanesulfonamidoethylaniline, 3-methoxy-
4-ami2 N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N, N-dimethylaniline, N-ethyl-N-β-[β-(β-methoxyethoxy)ethoxy]ethyl 3-Methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and salts thereof such as sulfates, salts, sulfites, p- ) luenesulfonate, phosphate, etc.

Furthermore, for example, JP-A-48-64932, JP-A-50-1
No. 31526, No. 51-95849, and Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 1100-3125 (195
1 year) are also listed as representative examples. The amount of the color developing agent that may be used in combination is not particularly limited, but the N-hydroxyalkyl-substituted-p-
The amount is preferably equal to or less than the same mole relative to the phenylenediamine conductor developing agent.

The color developing solution of the present invention has a bromide ion concentration of 5 x 10-'
It is preferable that the bromide ion concentration is molar or more, but in the present invention, a high bromide ion concentration is preferable because the amount of replenishment can be reduced.In conventional development systems, a low bromide ion concentration is preferable because it suppresses the development reaction. However, in the combination of the photographic element of the present invention and a color developing solution, on the contrary, it is preferable that the bromide ion concentration is high, so that the object of the present invention can be better achieved.

In other words, since the present invention is less affected by the bromide ion concentration, the amount of replenishment can be reduced.

The bromide ion concentration is preferably I x 10-'' mol or more, particularly preferably 1.5 x 10-'' mol or more. It is not preferable to use more than 10-2 moles. Note that the chloride ion concentration has no effect.

Next, one Fischer dispersion coupler of the present invention will be explained.

The Fischer dispersion coupler of the present invention preferably has at least one acidic group such as a sulfonic acid group or a carboxyl group, so that the coupler itself and the coloring dye do not diffuse in the hydrophilic colloid (in this case, it is preferable that the Fischer dispersion coupler has at least one acidic group such as a sulfonic acid group or a carboxyl group), and the coupler itself and the coloring dye do not diffuse in the hydrophilic colloid. (At least one organic group having 8 or more carbon atoms is allowed to exist as a preventing group at a non-active site, that is, at a position from which it will not be separated by the coupling reaction.) The total amount of couplers used in each emulsion layer may be selected as appropriate since the maximum concentration differs depending on the coloring property of each coupler, but it is approximately 0.01 to 0.5 mol per mol of silver halide. It is preferable to do so.

In order to disperse the Fischer dispersion coupler of the present invention in an alkaline aqueous solution, for example, the method described in JP-A No. 59-60437 may be employed.

In this case, since the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the wood-philic colloid as an alkaline aqueous solution.

The yellow coupler used as the Fischer dispersion coupler of the present invention is preferably one having pivaloylacetanilide as a core, and particularly preferably a yellow coupler represented by the following general formula (I).

General formula (1) R11 and RI2 may be the same or different, and include, for example, a hydrogen atom, a halogen atom, an alkyl group (e.g., methyl group, ethyl group, isopropyl group, etc.), an alkoxy group (e.g., methoxy group, ethoxy group, etc.). group, methoxyethoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.)
, acylamino group (e.g. acetylamino group, trifluoroacetylamino group, etc.), sulfonamino group (e.g. methanesulfonamino group, benzenesulfonamino group, etc.), carbamoyl group, sulfamoyl group, alkylthio group, alkylsulfonyl group, alkoxycarbonyl group ,
Examples include ureido group, carboxyl group, hydroxy group, sulfo group, and cyano group.

As a Fischer dispersion coupler, at least one of R11 to R12 has a diffusion preventing group (for example, a group having 8 or more carbon atoms such as a dodecyl group), and R11, RI2, and x1□
At least one of them contains at least one acidic group (eg, carboxyl group, sulfo group, etc.). X
Examples of ll include a hydrogen atom, a halogen atom, and those represented by the following general formula.

General formula In this general formula, A represents an oxygen element or an oxygen atom,
B represents a nonmetallic atom necessary to form an aryl ring or a heterocycle, and E represents a nonmetallic atom necessary to form a 5- or 6-membered heterocycle together with a nitrogen atom. These i may further be fused with an asol ring or a hetero ring.

D represents an organic group (for example, an alkyl group, an aryl group) or an atom (for example, a halogen atom), and b represents 0 or a positive integer. When b is plural, D may be the same or different, D is 10-, -5-1-COO-, -CONH
--3O2NH-1-N)ICONll-1-SO,-
1-CO-1-NH(:0-1-OCO-5-N)IS
It may contain a linking group such as O□-1-N13-.

Further, as the Fischer dispersion coupler of the present invention, one having benzoylacetanilide as a core is also preferable, and a yellow coupler represented by the following general formula (n) can be used.

General formula [■] (R1ff, R14, Rla, and R16 are substituent components (substituents or atoms such as hydrogen atoms), It is preferably a yellow coupler represented by (a group or atom that can be separated by reaction).

For example, hydrogen atoms, halogen atoms, alkyl groups (e.g., methyl, ethyl, isopropyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, methoxyethoxy, etc.), aryloxy groups (e.g., phenoxy group, etc.), acylamino group (eg, acetylamino group, trifluoroacetylamino group, etc.), sulfonamino group (eg, methanesulfonamino group, benzenesulfonamino group, etc.), carbamoyl group.

Examples include sulfamoyl group, alkylthio group, alkylsulfonyl group, alkoxycarbonyl group, ureido group, carboxyl group, hydroxy group, sulfo group, and cyano group.

As the Fischer dispersion coupler of the present invention, R13 to R
At least one of I6 has a diffusion-preventing group (e.g., a group having 8 or more carbon atoms, such as a dodecyl group), and at least one of R12 to RIG and Lx contains an acidic group (e.g., a carboxyl group, a sulfo group, etc.) used. X12 is X
It has the same meaning as ll, and includes, for example, a hydrogen atom, a halogen atom, and those represented by the following general formula.

The magenta coupler as a Fischer dispersion coupler used in the present invention has the following general formulas (m) and (IV
) is preferably one having 1-phenyl-5-pyrazolone or pyrazolobenzimidazole as a core.

General formula (III) General formula [■] Here,
Both BIT and R11l are the above-mentioned R1+ and also X
1ff has the same meaning as xl□ described above.

In the above general formulas (III) and (rV), R17 is, for example, an acylamino group (e.g. propaneamyl-
R16 includes, for example, a hydrogen atom, a halogen Examples thereof include atoms, alkyl groups, alkoxy groups, hydroxycarbonyl groups, alkoxycarbonyl groups, nitro groups, aryloxy groups, sulfo groups, carboxyl groups, cyano groups, and acylamino groups.

The Fischer dispersion coupler of the present invention is R□7,
At least one of R111 has a diffusion preventing group (for example, a group having 8 or more carbon atoms such as a dodecyl group), and R1? , R
Those containing at least one of la and X1ff or at least one acidic group (eg, carboxyl group, sulfo group, etc.) are used. The X1ff may be the same as the above-mentioned X11. f is an integer from 0 to 4, and when " is 2 or more, each R18 may be the same or different.

In addition to the above, preferred magenta couplers as Fischer dispersion couplers used in the present invention are those having pyrazolotriazole as a core, and particularly those having the general formula (V) 2G (provided that R, , -J-R2゜ and R□ is a magenta coupler represented by the above-mentioned R++, and X14 is the same as the above-mentioned Xll. R+9,
R2° is, for example, a hydrogen atom, an alkyl group which may have a substituent (e.g., methyl group, ethyl group, isopropyl group, propyl group, butyl group, etc.), an aryl group (e.g., phenyl group, naphthyl group, etc.), or represents a telocyclic residue, J represents a bond, such as -〇-1-3-, -N-,
R22 represents a hydrogen atom or an alkyl group t, and R21 represents, for example, a hydrogen atom.

As the Fischer dispersion coupler of the present invention, RI9 to R
At least one of 21 has a diffusion-preventing group (e.g., a group having 8 or more carbon atoms, such as a dodecyl group), and at least one of RI9 to L+ and X14 has at least one acidic group (e.g., a carboxyl group, a sulfo group, etc.) Included is used. As XI4, a hydrogen atom, a halogen atom, and a group of the following general formula are preferable.

General Formula In this general formula, R13 is a halogen atom, an alkyl group (e.g. methyl group, ethyl group, etc.), an alkoxy group (
For example, methoxy group, ethoxy group, etc.), acylamino group (
For example, acetamido group, benzamide group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group, etc.), anilino group (for example, 2-chloroanilino group, 5-acetamidoanilino group hJ), N-alkylcarbamoyl group (
For example, N-methylcarbamoyl group, etc.), ureido group (for example, N-methylureido group, etc.), cyano group, aryl group (for example, phenyl group, naphthyl group, etc.), N,N-dialkylsulfamoyl group, nitro group, hydroxy When 1g is 2 or more, R2 and R3 may be the same or different.

R24 represents a substituted or unsubstituted alkyl group (e.g., butyl group, methyl group, etc.), an aralkyl group (e.g., benzyl group, etc.), an alkenyl group (e.g., allyl group, etc.), or a cyclic alkyl group (e.g., cyclopentyl Examples of groups include halogen atoms, alkoxy groups (butoxy groups, methyloxy groups, etc.), acylamino groups (e.g. acetamido groups, tetradecanamide groups, etc.), alkoxycarbonyl groups (e.g. methoxycarbonyl groups, etc.), N-alkylcarbamoyl groups (e.g. N -methylcarbamoyl group, etc.)
, ureido group (e.g. ethylureido group etc.), cyano group, aryl group (e.g. phenyl group etc.), nitro group, alkylthio group (e.g. methylthio group etc.), alkylsulfamoyl group (e.g. ethylsulfamoyl group etc.), It is selected from alkylsulfone groups, anilino groups, sulfonamide groups (for example, ethylsulfonamide groups, etc.), N-alkyl-containing ulfamoyl groups, aryloxy groups, and acyl groups (for example, acetyl groups, etc.).

The cyan coupler that can be used as the Fischer dispersion coupler of the present invention is preferably one having phenol or naphthol as a core, particularly those represented by the following general formulas (VI) and (■).
The following can be mentioned.

General formula (VT) 0 ■ General formula [■] In this general formula, R5 to Rm are all Ru
Also, Xss and XIj are synonymous with the above-mentioned Xu.

R25 is 1, for example, a hydrogen atom, an aliphatic group (for example, an alkyl group such as an ethyl group, an isopropyl group, an acyl group, a cyclohexyl group, an octyl group, etc.), an alkoxy group (
For example, methoxy group, isopropoxy group, pentadecyloxy group, etc.), aryloxy group (for example, phenoxy group, β
-tert-butylphenoxy group, etc.), an acylamide group, a sulfonamide group, a ureido group, or a carbamoyl group represented by the following general formula.

General formula % formula % In the formula, G1. G2 may be the same or different, and each represents a hydrogen atom (however, Gu and Gz are not hydrogen atoms at the same time), an aliphatic group having 1 to 8 carbon atoms, preferably a C 4 to 8 aliphatic group. Straight chain or branched alkyl groups, cyclic alkyl groups (e.g. cyclopropyl group, cyclohexyl group, norbornyl group, etc.) or aryl groups (e.g. phenyl group,
naphthyl group, etc.), where the alkyl group and aryl group above represent a halogen atom (e.g. fluorine, chlorine, etc.), nitro group, cyano group, carboxyl group, sulfo group, hydroxy group, amino group (e.g. ami/group, alkyl group, etc.). (amino group, dialkylamino group, anilino group, toalkylanilino group, etc.), alkyl group (e.g., those mentioned above): alkoxycarbonyl group (e.g., butyloxycarbonyl group, etc.)
Acyloxycarbonyl group, amide group (e.g. acetamide group, methanesulfonamide group, etc.), imide group (e.g. succinimide group, etc.), carbamoyl group (e.g. N,
N-diethylcarbamoyl group, etc.), sulfamoyl group (
For example, N,N-diethylsulfamoyl group, etc.), alkoxy group (e.g., ethoxy group, butyloxy group, octyloxy group, etc.), aryloxy group (e.g., phenoxy group, methylphenoxy group, etc.), etc. may be substituted. .

In addition to the above-mentioned substituents, R3 may contain commonly used substituents.

Rn is selected from, for example, a hydrogen atom, an aliphatic group, especially an alkyl group, or a carbamoyl group represented by the above general formula.

R2? , Rn, Rzs, R depth and R depth are, for example, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylthio group, a heterocyclic group, an amino group, a carbonamide group, a sulfonamide group, a sulfamyl group, or Examples include carbamyl group.

Specific examples of R27 include the following.

i.e. hydrogen atoms, halogen atoms (e.g. chloro, bromine, etc.), primary, secondary or tertiary alkyl groups (e.g. methyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl). , hexyl group, 2-chlorobutyl group, 2-hydroxyethyl group, 2-phenylethyl group, 2-(2,4,8-trichlorophenyl)ethyl group,
2-7minoethyl group, etc.), alkylthio group (e.g. octylthio group, etc.), aryl group (e.g. phenyl group, 4-
Methylphenyl group, 2,4.8-trichlorophenyl group, 3.5-dibromophenyl group, 4-trifluoromethylphenyl group, 2-tolylfluoromethylphenyl group,
3-trifluoromethylphenyl group, naphthyl group, 2-
chloronaphthyl group, 3-ethylnaphthyl group, etc.), heterocyclic groups (e.g. benzothiazolyl group, penzoxazolyl group, naphthoxacylyl group, pyridyl group, xalyl group, etc.), amino groups (e.g. amine group, methylamine group) , diethylamino group, phenylamino group, tolylamino group, 4
-cyanophenylamine 7m, 2-trifluoromethylphenylamino group, benzothiazole amino group, etc.), carbonamide group (for example, alkylcarbonamide group such as ethylcarbonamide group; phenylcarbonamide group,
2,4.6-trichlorophenylcarbonamide group,
2-Ethoxycarbonamide group; heterocyclic carbonamide group such as thiazolecarbonamide group, benzothiazolecarbonamide group, oxacylylcarbonamide group, benzoxacylylcarbonamide group, imidazolylcarbonamide group, benzimidazolylcarbonamide group, etc. ), sulfonamide groups (e.g. butylsulfonamide groups).

Alkylsulfonamide group such as phenylethylsulfonamide group: phenylsulfonamide group.

2.4.8-trichlorophenylsulfonamide group, 2
- Arylsulfonamide groups such as diphenylsulfonamide diphenylsulfonamide groups; thiazolylsulfonamide groups, benzothiazolylsulfonamide groups, imidazolylsulfonamide groups,
Heterocyclic sulfonamide groups such as benzimidazolylsulfonamide groups and pyridylsulfonamide groups), sulfamyl groups (alkylsulfamyl groups such as propylsulfamyl groups and octylsulfamyl groups; phenylsulfamyl groups, Arylsulfamyl groups such as 2,4.8-1-lichlorophenylsulfamyl group and 2-methoxyphenylsulfamyl group: thiazolylsulfamyl group, benzothiazolylsulfamyl group, oxacylylsulfamyl group group, benzimidazolylsulfamyl group,
heterocyclic sulfamyl groups such as pyridylsulfamyl group) and carbamyl groups (alkylcarbamyl groups such as ethylcarbamyl group and octylcarbamyl group; phenylcarbamyl group, 2,4.8-trichlorophenylcarbamyl group) Arylcarbamyl groups and thiazolylcarbamyl groups, benzothiazolylcarbamyl groups, oxacylylcarbamyl groups, imodazolylcarbamyl groups,
a heterocyclic carbamyl group such as a benzimidazolylcarbamyl group, etc.).

Rn, Rzs, Rx and R21 can also specifically include those listed in R27, and j
represents a nonmetallic atom necessary to form a 5- and/or 6-membered ring as shown below. Namely, examples thereof include a benzene ring, a cyclohexene ring, a cyclopentyl ring, a thiazole ring, an oxazole ring, an imidazole ring, a pyridine ring, and a pyrrole ring. Among these, a benzene ring is preferred.

The Fischer dispersion coupler of the present invention has the general formula [
■ In]. At least one of Rs, RrrNR
has a diffusion-preventing group (for example, a group having 8 or more carbon atoms such as a dodecyl group), and R25, R2? Those in which at least one of ~R3 and Xi5 contains at least one acidic group (eg, carboxyl group, sulfo group, etc.) are preferably used.

The Fischer dispersion coupler of the present invention has the general formula [
(2), at least one of Ihs-Rn has a diffusion-preventing group (for example, a group having 8 or more carbon atoms such as a dodecyl group), and at least one of R2s''Rrl and Xxs has an acidic group (for example, a carboxyl group, a sulfo group). etc.) are preferably used.

Xi. X* is preferably a hydrogen atom, a halogen atom and -
Groups bonded to the coupling position via 〇-, -S-, -N-N- (for example, alkyl groups, aryl groups, heterocyclic groups, etc.) are preferred as such groups, such as alkoxy groups and aryl groups. These include oxy, alkylthio, and arylthio groups. These groups are further 10-, -S-
, -N)I-, -CONH- -COO-, -S02
NH-, -SO-, -SOz-, -GO-
may have a substituent (for example, an alkyl group, an aryl group, a heterocyclic group, etc.) via a divalent group such as . Furthermore, these groups may have a carboxyl group, a sulfo group, a sulfamoyl group, a hydroxy group, etc. as a substituent.

Typical specific examples of the Fischer dispersion coupler of the present invention are listed below.

[Exemplary compounds]

IH I-C! OOH H I Go (JH Y-10 at at 17H35 H350i7-0-CH2 II I O3H O3H t M-11 M-13ct t t I OOH M-t8 0t b H t t t m9 H OCH2CH2CoOH H H o 3Na H H O3H These Fischer dispersion couplers of the present invention may be used alone or in combination of two or more types.When such two or more types are used in combination, the quantitative ratio does not matter.

In the photosensitive silver halide emulsion layer of the present invention, one or more oil droplet dispersion couplers may be used together with the Fischer dispersion coupler of the present invention. And when they are used together, the quantitative ratio does not matter.

Oil droplet-dispersed yellow couplers that can be used in combination with the present invention include open chain ketomethylene compounds, active point -〇-aryl substituted couplers called so-called 2-equivalent type couplers, active point -〇-acyl substituted couplers, and active point hydantoin compound substituted couplers. , active point urazole compound substituted couplers, active point substituted couplers with cohelic acid imide compounds, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -〇-sulfonyl substituted couplers, and the like.

In addition, oil droplet-dispersed magenta couplers that can be used in combination in the present invention include pyrazolone-based, pyrazolotriazole-based,
Examples include pyrazolinobenzimidazole and indacylon compounds. These oil droplet-dispersed magenta couplers, like the yellow couplers, are not limited to 4-equivalent type couplers, and may also be 2-equivalent type couplers.

Furthermore, examples of oil droplet-dispersed cyan couplers that can be used in combination in the present invention include phenol-based and naphthol-based couplers. These oil droplet-dispersed cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers.

The processing method for the photographic element of the present invention can 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 the processing liquid is atomized, a web method in which contact is made with a carrier impregnated with the processing liquid, or a developing method using a viscous processing liquid, etc. Processing schemes can be used.

In addition to the above, there are no particular limitations on the processing method for the photographic element of the present invention, and any processing method can be applied.For example,
Typical methods include bleach-fixing after color development, followed by further washing and/or stabilization treatment if necessary. 1 After color development, bleaching and fixing are carried out separately, and further washing and/or stabilization are carried out if necessary. or a method of stabilizing treatment;
Alternatively, a method of pre-hardening, neutralization, color development, stop fixing, water washing, bleaching, fixing, water washing, post-hardening, water washing, color development, water washing, supplementary color development, stopping, bleaching, fixing, water washing, Any method may be used for processing, such as a method in which 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.

The color developer 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! Other agents, thickeners, development accelerators, etc. can also be optionally included.

Examples of additives other than the above added to the color developer include bromides such as potassium bromide and sodium bromide, alkali iodides, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole,
In addition to compounds for rapid processing solutions such as 1-phenyl-5-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-mentioned 7-minopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylene diaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid glycol ether diaminetetraacetic acidethylenediaminetetrapropionic acidethylenediaminetetraacetic acid disodium saltdiethylenetri7minepentaacetic acid pentasodium saltnitrilotriacetic acid sodium saltBleaching solutions are various in addition to the above bleaching agents. 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. In addition, the bleach-fix solution may further contain a halogen compound such as potassium bromide, and as in the case of the above-mentioned bleach solution, various other additives such as pH 1i buffer, optical brightener, Adding antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc.
It may be included.

The silver halide fixing agent is 1, 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.

From the viewpoint of rapid processing, the processing temperature of the photographic element of the present invention in various processing steps other than color development, such as bleach-fixing (or bleaching, fixing), washing with water and stabilization as necessary, is also 30°C. It is preferable to carry out the above.

The photographic element of the present invention is disclosed in JP-A-58-14834, JP-A-58-14834;
-105145, 58-134634 and 58
-18631 and Japanese Patent Application No. 58-2709 and No. 5
A stabilization treatment as an alternative to water washing as shown in No. 9-89288 or the like may be performed.

To explain silver halide grains in more detail, the crystals of silver halide grains may be normal crystals, twin crystals, or other crystals.
, Any ratio between the [1,0,0] plane and the [1,1,1] plane can be used. Furthermore, 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. 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. 59-
170070) can also be used.

Silver halide grains particularly preferably used in the present invention are:
It is substantially monodisperse, and may be obtained by any preparation method such as an acidic method, a neutral method, or an ammonia method.

Alternatively, for example, seed grains may be produced using an acidic method, and then grown using an ammonia method, which has a fast growth rate, to grow to a predetermined size. control etc.,
For example, it is preferable to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains, 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, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothiol-3-
Sensitizers such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chloroparadate, potassium chlorooleate and sodium chlorovaladate (these These substances act as sensitizers or fog suppressants depending on the amount. It may also be chemically sensitized (for example, in combination with a sensitizer).

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, a nitrogen-containing emulsion having at least one hydroxytetrazaindene and mercapto group is produced. It may also contain at least one type of terocyclic compound.

The silver halide used in the present invention is mixed with an appropriate sensitizing dye in an amount of 5 X 10-' to 3 X 1 per mole of silver halide in order to impart photosensitivity to a desired wavelength range.
Optical sensitization may be achieved by adding G-'' moles.

Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more types. Examples of the sensitizing dyes that can be advantageously used in the present invention include the following: I can list kimono.

That is, as sensitizing dyes used in blue-sensitive silver halide emulsions, for example, West German Patent No. 929,080 and U.S. Pat.
, No. 231,658, No. 2,493,748, No. 2,
No. 503.776, No. 2,519,001, No. 2,9
No. 12,329, No. 3.656,959, No. 3,67
2.1197, 3,694,217, 4,02
No. 5,349, No. 4,046,572, British Patent No. 1,
No. 242.588, Special Publication No. 44-14030, No. 52
-24844 etc. can be mentioned. In addition, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.
, No. 072,908, No. 2,739,149, No. 2,
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 945.763, British Patent No. SO5,979, and the like. Furthermore, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Pat.
No. 4, No. 2,270,378, No. 2,442,710
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent No. 2,454,629, No. 2,776.280, and the like. Furthermore, U.S. Patent 2,213,99
No. 5, No. 2,493,748, No. 2,519,001
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 929.080 and others 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 element 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.

A typical particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 6, No. 43-22884, No. 45-18433,
No. 47-37443, No. 48-28293, No. 49
No.-6209, No. 53-12375, JP-A-52-2
No. 3931, No. 52-51932, No. 54-8011
No. 8, No. 58-153926, No. 59-116646
No. 51-116647 and the like.

Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-11
No. 114, No. 47-25379, No. 48-38406
No. 48-38407, No. 54-34535, No. 55-1569, JP-A-50-33220, No. 50
-38526, 51-107127, 51-1
No. 15820, No. 51-135528, No. 52-10
No. 4916, No. 52-104917, and the like.

Furthermore, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication Nos. 44-32753 and 46
-11627, JP-A No. 57-1483, and regarding merocyanine, for example, JP-A No. 4G-38408.
No. 48-41204, No. 50-40662, JP-A No. 56-25728, No. 5B-10753, No. 5
B-91445, No. 59-116645, No. 50-
No. 33828 etc. are mentioned.

Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publications Nos. 43-4932, 43-4933, 45-26470, and 46
-18107, No. 47-8741, JP-A-59-1
No. 14533, etc., and the method described in Japanese Patent Publication No. 49-6207, which uses zeromethine or dimethine merocyanine, monomethine or trimethine cyanine, and styryl dye, can be advantageously used.

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, or acetone is prepared in advance.

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 addition may be made 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.

In the silver halide emulsion layer of the present invention and other photographic constituent layers, couplers such as a non-diffusible DIR compound, a sicard magenta cyan coupler, a polymer coupler, and a diffusible DIR compound may be used in combination. The compound, colored magenta or cyan coupler is described in Japanese Patent Application No. 59-193611 by the present applicant, and the poly7-coupler is described in Japanese Patent Application No. 59-198 by the present applicant.
72151 can be referred to.

In one or more of the photographic constituent layers of the photographic element of the present invention, a dye (AI dye) that is water-soluble or decolorable with a color developing solution is used.
can be added, and the AI 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 British Patent No. 584,
No. 609, No. 1,277.429, Japanese Unexamined Patent Publication No. 48-85
No. 130, No. 49-99620, No. 49-11442
No. 0, No. 49-129537, No. 52-108115
No. 59-25845, No. 59-111640,
No. 59-111641, U.S. Patent No. 2.274,782
No. Z, No. 533,472, No. 2,956,879
No. 3,125,448, No. 3,148,187, No. 3,177.078, No. 3,247,127,
No. 3,260,601, No. 540,887, No. 3,575,704, No. 653,905.

Examples include those described in No. 3,718,472, No. 4,071,312, and No. 4,070,352.

These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use X 1G-' to 5 x 10-' moles, more preferably l x 10-2 to I X 1
0-' mole is used.

In addition to the above, the photographic elements of the present invention may contain various photographic additives, such as antifoggants, stabilizers, ultraviolet absorbers, and colorants as described in Research Disclosure 1764:1. Anti-staining agents, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used.

In the photographic elements of this invention, the woody colloids used to prepare the emulsions include gelatin, derivative gelatins, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethyl cellulose derivatives, carboxylic Any of cellulose derivatives such as methyl cellulose, starch derivatives, single or copolymer synthetic wood-philic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide are included.

Supports for the photographic elements of the invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or with a reflector, such as glass plates, cellulose acetate, cellulose nitrate, or Examples include polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc., and other ordinary transparent supports may be used, and these supports are appropriately selected depending on the intended use of the photographic element. .

For coating the silver halide emulsion layer and other photographic constituent layers used in the present invention, a number of coating methods can be used, such as dipping coating, air doctor coating, curtain coating, and hopper coating. Also, U.S. Patent No. 2,761
, No. 791 and No. 2,941,898 can also be used to simultaneously coat two or more layers.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily.For example, in the case of vapor for full color printing, from the support side, the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, It is preferable to arrange the red-sensitive silver halide emulsion layers. Each of these photosensitive silver halide emulsion layers may consist of two or more layers.

In the photographic element of the present invention, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a storage layer, and an antihalation layer can be used in appropriate combinations as photographic constituent layers. 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.

The photographic element of the present invention is a multilayer color photographic element having at least three layers including each of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer. Not only the emulsion layer but also the intermediate layer,
Refers to all hydrophilic colloid layers on the side coated with a photosensitive emulsion layer, such as an overcoat layer and a subbing layer. In this specification, they have the same meaning. ) The thickness of the gold film is 147L when dry.
It is preferably 11 or less, more preferably 13JLs or less.

Particularly preferably, it is 12 pm or less.

[Effects of the Invention] According to the present invention, even when processing is performed using a single color developer with a low replenishment amount, it is not affected by changes in bromide ion concentration, and is not affected by changes in processing concentration and PTI value of the single color developer. It is possible to maintain constant proper photographic performance over a long period of time without any damage.
Moreover, it is possible to provide a rapid and stable method for processing photographic elements in which the coloring dyes and uncolored areas obtained do not fade or change color even after long-term storage.

[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 samples Nos. 001 to 15. Table 1 shows the emulsion composition and coupler of each sample.

R1---1,2 g/d gelatin, 0.27 g/n
f ([conversion, the same applies hereinafter) average grain size 0.5 (L melon blue-sensitive silver halide gelatin emulsion (silver chlorobromide emulsion, the silver bromide content is shown in Table 1), yellow coupler (coupler The type and method of addition are shown in Table 1.) A blue-sensitive silver halide emulsion layer containing:

Layer 2---0.70g/m2 gelatin, 106/r
n' anti-irradiation dye (AI-1), 5+g
/m'' (AI-2).

Layer 3---1.25g/rr1' gelatin, 0.
A green-sensitive silver halide gelatin emulsion (a silver chlorobromide emulsion, the silver bromide content is shown in Table 1) with an average grain size of 28 g/m' 0.35 pII+, a magenta coupler (the type of coupler and the method of addition are shown in Table 1). A green-sensitive silver halide emulsion layer containing ) shown in FIG.

Layer 4---1.2 g/rn' gelatin, 0.6 g/m
An intermediate layer consisting of a UV absorber (UV-1).

Layer 5---1.4 g/rn' gelatin, 0.20
g/m', average grain size OjS Kawara red-sensitive silver halide gelatin emulsion (silver chlorobromide emulsion, silver bromide content is shown in Table 1), cyan coupler (type of coupler and addition method are shown in Table 1). A red-sensitive silver halide emulsion layer containing 1).

Layer 6---0.50g/m'' gelatin, 0.3g/m''
A protective layer consisting of a UV absorber (UV-1') of rn'.

Layer 7: Protective layer containing 0.90 g/rn'' gelatin.

The silver halide used 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 color-sensitized with a general sensitizing dye.

*4 Each coupler YY-1, MM-1, and CG-1 was dissolved in a mixed solvent of dioctyl 7-thaletate and ethyl acetate, and then dissolved in gelatin 10% to which Alkanol XC (manufactured by Devon) was added as a surfactant. % aqueous solution,
It was emulsified and dispersed using a colloid mill and added to a silver halide gelatin emulsion.

Each coupler Y-1, Y-2, M-1, C-1 is IN
After dissolving in a caustic potassium aqueous solution, it was added to a 10% gelatin aqueous solution, the pH was adjusted to 7.0 with an IN citric acid aqueous solution, and the mixture was added to a silver halide gelatin emulsion.

The amounts of each coupler added were 0.40 mol of yellow coupler, 0.20 mol of magenta coupler, and 0.40 mol of cyan coupler per 1 mol of silver halide.

The total amount of the 52 types of couplers added is the above addition ff (
Q: I made it so that the amount was 40 mol. The addition ratio of each coupler is a molar ratio.

α'y-i) t (MM-1) L (AI-1) (AI-2) (UV-1) 04Hp(t) In addition, as a hardening agent, 2,4-dichloro-6-humanroxy S -)-Sodium lyazine was added to layers 2, 4 and 6 at a rate of 0.02 g/g of gelatin, respectively.

Each of samples No. 1 to 15 shown in Table 1 was exposed through an optical wedge and then processed in the following steps.

Processing process (38℃) Color development 120 seconds bleach fixing 60 seconds washing 60 seconds drying
50-80°C for 120 seconds The composition of each treatment solution is as follows.

[Color developer] Pure water 800 Holitate benzyl alcohol lSm1 sulfuric acid hydroxyamine 2.0g Potassium bromide
0.5g sodium chloride
1. (Ig potassium sulfite
2.0g triethanolamine
2.0g color developing agent (as shown in Table 1)
0.023 mol l-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5 m
l Magnesium chloride 0.3g Potassium carbonate 32g Kaycol
l-PK-Cone (fluorescent brightener, manufactured by Shin Nisso Kako Co., Ltd.) 2. Add pure water to make one sentence and adjust the pH with 20% potassium hydroxide or 10% dilute sulfuric acid.
= Adjust to 10.1.

[Bleach-fix solution] Pure water 550 votes Iron ethylenediaminetetraacetate (m) Ammonium salt 65g Ammonium thiosulfate (70% aqueous solution) 85g Sodium hydrogen sulfite 10g Sodium metabisulfite
19. Add 2g of ethylenediaminetetraacetic acid-disodium and 20g of pure water. Bind and use ammonia water or dilute sulfuric acid to pl = 7.0 51! ! do.

Separately, the potassium bromide concentration Q-5g/gram of the color developer is 1.5g/9. The same sample No.
-15 were each subjected to development processing.

Sensitometry was performed on each sample obtained by a conventional method. Table 2 shows the change in color density when the potassium bromide concentration was varied at an exposure amount of 1.0 for the color density of each sample when the potassium bromide concentration was 0.5 g/l. Here, ΔD in Table 2 is the color density when potassium bromide Q-5g/l and potassium bromide 3.5g/! This is the difference from the color density at L, and represents the magnitude of the change in photographic performance when the potassium bromide concentration changes.

Below is a color developing agent for margin comparison [CD-3]: 3/2H2SO4.H20 As is clear from the results in Table 2, 1 In the case of processing using the color developing agent of the present invention 1 Sample No. 7 to 15 of the present invention It can be seen that the color development density change due to the KBr concentration fluctuation was small, indicating that the change in photographic performance was very small.

On the other hand, when a color developing agent other than the present invention (CD-3) was used, compared to comparative samples Nos. 1 to 6, sample No. of the present invention,
In Samples 7 to 15, the change in color density due to a 6 degree change in KBr is small, but it can be seen that the change in color density during improvement is smaller compared to the color developing agent of the present invention.

Examining the results in Table 2 in more detail, the following can be said.

Comparing samples in which the couplers had exactly the same composition but differed only in the silver bromide content of green-sensitive silver halide emulsions and red-sensitive silver halide emulsions, it was found that in the case of the developing agent or the sulfate of exemplified compound (1), the couplers were in accordance with the present invention. Also in the case of the oil droplet dispersion coupler, when the silver bromide content of the above emulsion is 5 to 65 mol, K
It can be seen that although the change in photographic performance with respect to Br variation is small, it is greatly improved when the coupler of the present invention is used in at least one layer. It can be seen that even when the developing agent is CD-3, although changes in photographic performance are improved when the emulsion of the present invention and the coupler of the present invention are used, the effect is small compared to the developing agent of the present invention. .

Therefore, it can be seen that the effects of the present invention can be obtained only when the silver bromide content of the green-sensitive and red-sensitive silver halide emulsions, the type of color developing agent, and the type of coupler are satisfied.

Note that Table 2 shows that as the bromide ion concentration increases, the amount of replenishment is reduced, which indicates that the treatment of the present invention can significantly reduce the amount of replenishment.

Example 2 Using samples Nos. 1 to 15 of Example 1, the dependence of photographic performance on pH fluctuations of the color developer was evaluated.

The potassium bromide concentration of the color developer of Example 1 was adjusted to 1.3 g/
The color developing agent has a PTT of 9.8, 10 for a 0 color developer using the sulfate of Exemplary Compound (1), an N-hydroxyalkyl-substituted p-phenylenediamine derivative.
．． 2. Processed in exactly the same manner as in Example 1 except that l016 was used (
The potassium bromide moisture content of the color developing solution was determined (0.5 g/IL), and sensitometry was evaluated. The results obtained are shown in Table 3.

In the table, the yellow density shows the movement of the color density when the pH is changed at the exposure amount that gives a color density of 1.0 when developed at pHL (J, 2). This indicates the magnitude of the change in photographic performance when the pH changes.The color density is measured using a spectral reflection densitometer (
Table 3 shows only the yellow density measured using PI) A-65) manufactured by Konishiroku Photo Industry Co., Ltd.

As is clear from the results in Margin Table 3 below, Sample No. 1 of the present invention, No. 7
~15, it can be seen that the concentration change is extremely small with respect to the fluctuation of pH 9.8 to pH 10.6. Therefore, it was found that the samples of the present invention had significantly improved changes in photographic performance with respect to po fluctuations.

Example 3 Samples Nos. 1 to 15 of Example 1 were used to evaluate the dependence of photographic performance on temperature fluctuations of the one-color developer.

The potassium bromide concentration of the color developer of Example 1 was adjusted to 1.3 g/
! The temperature of the 0 color developer using the sulfate of exemplified compound (1) of tohydroxyalkyl-substituted p-phenylenediamine salt conductor was 33°C, 36°C, and 40°C. The treatment was carried out in exactly the same manner as in Example 1 (potassium bromide concentration of color developer: 0.5 g/R), and sensitometry was evaluated. The results obtained are shown in Table 4.

In the table, the yellow density shows the movement of the color density when the temperature is varied at the exposure amount that gives a color density of 1.0 when developed at a temperature of 36°C. ΔD is the change in color density, and represents the magnitude of the change in photographic performance when pt+ changes. The color density was measured using a 1-spectral reflection densitometer (PDA-65 manufactured by Konishiroku Photo Industry Co., Ltd.), and only the yellow density is shown in Table 4.

Margin Table 4 Below: As is clear from the results in Table 4, Sample No. 7 of the present invention
It can be seen that for samples 15 to 15, the concentration change was extremely small with respect to temperature fluctuations of 33°C to 40°C. Therefore, the sample of the present invention has a pH of
It was found that the change in photographic performance with respect to fluctuations was significantly improved.

Example 4 Samples No. 12 of Example 1 were exposed and developed in the same manner as in Example 1 using the same processing solution.

The color developing solution was prepared by changing the color developing agent as shown in Table 3, and the zero color development time used for processing was changed as shown in Table 3. The treatment temperature was 38°C.

The obtained sample was stored under irradiation with a xenon lamp, and changes in cyan concentration were measured. That is, when the initial sample concentration of 1.0 when CD-3 was used as the color developing agent deteriorated by about 0.3 for each processing time, the same concentration range of the sample treated with other color developing agents decreased. The concentration reduction was measured and shown in Table 5. At this time, the yellow stain density of the unexposed area of the same sample was measured and similarly shown in Table 5.

Comparative color developing agent [:CD-6] As is clear from the results in Table 5, when the color developing solution uses CD-3 or CD-6 as the color developing agent, how many seconds does the color development time take? However, there is no significant difference in the rate of fading, and it can be seen that the fading of CD-6 is greater than that of CD-3. This also applies to the yellow stain density (Dmin) of the unexposed area.

On the other hand, when the color developing agent of the present invention is Exemplified Compound (1), when the color development processing time is 180 seconds or more, the color fading is large and the storage stability is extremely low. The same can be said of Dmin).

However, when the color development time is 150 seconds or less, the storage stability is rapidly improved, and compared to the case of using the above (:D-3),
It can be seen that this gives a more favorable result. This is surprising considering that the structure of artificial color dyes is said to be closely related to the stability of the dye, and it is predicted that the residual amount of the color developing agent in the film may also be closely related. be done.

October 27, 1985 Mr. Akio Kuroda, Commissioner of the Patent Office 1 Indication of the case Patent Application No. 1983-232127 2 Name of the invention Processing method for silver halide color photographic light-sensitive materials 3 Amendment Relationship with the case of a person who does Spontaneous 6. Number of inventions increased by amendment Contents of amendment (Japanese Patent Application No. 60-2:32127) The description is amended as follows.

1. In lines 2 to 1 from the bottom of page 24, the phrase "the smaller the better," is corrected to "the smaller the better."

2 Correct r (R+a)4J in [General formula (■)] on page 41 to r (R+a)rJ.

3 Correct r(Rxa), , J in (general formula (■)) on the same page to r(Rsa)fJ.

4. Correct “゛” in the structural formula rY-7J on page 57.

5 rN in the structural formula “Y-8, Y-9” on page 58
N rN NCH3CN.

1”. and correct each.

6. In the first line of page 97, "(as shown in Table 1)" is corrected to "(as shown in Table 2)".

7. On page 103, line 1 and page 105, lines 15 to 16, it says, “(Potassium bromide concentration of color developer: 0.5 g/fL.
) Delete J and each.

8. On page 108, line 4, it says "rpH fluctuation" and is corrected to "temperature fluctuation".

that's all

Claims (12)

[Claims] (1) In a method for developing a silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, at least The silver halide emulsion of the red-sensitive silver halide emulsion layer has a silver bromide content of 5 to 6.
A silver halide color photographic light-sensitive material which is substantially 0 mol% silver chlorobromide emulsion and in which at least one light-sensitive silver halide emulsion layer contains a Fischer dispersion coupler;
Using a color developing solution containing an N-hydroxyalkyl-substituted-p-phenylenediamine derivative,
A method for processing a silver halide color photographic material, which is characterized by developing in seconds or less. (2) A method for processing a silver halide color photographic material according to claim 1, wherein the processing time is 120 seconds or less. (3) A method for processing a silver halide color photographic material according to claim 1, wherein the processing time is 90 seconds or less. (4) Claim 1, characterized in that the silver halide emulsion of at least one photosensitive emulsion layer is a substantial silver chlorobromide emulsion with a silver bromide content of 50 mol% or less. section,
A method for processing a silver halide color photographic light-sensitive material according to item 2 or 3. (5) The silver halide color according to any one of claims 1 to 4, wherein the total coating amount of silver in the silver halide color photographic light-sensitive material is 1 g/m^2 or less. Method of processing photographic materials. (6) Claim 1, characterized in that the color developer contains at least 5 x 10^-^3 moles of bromide.
A method for processing a silver halide color photographic material according to any one of items 1 to 5. (7) Claim 6, characterized in that processing is performed with a color developing solution containing 1 x 10^-^2 moles or more of bromide.
A method for processing a silver halide color photographic light-sensitive material as described in . (8) A method for processing a silver halide color photographic light-sensitive material according to claim 6, which comprises processing with a color developing solution containing 1.5 x 10^-^2 moles or more of bromide. (9) The method for processing a silver halide color photographic material according to claim 5, characterized in that the total amount of coated silver is 0.8 g/m^2 or less. (10) Claims 1 to 3, characterized in that the N-hydroxyalkyl-substituted p-phenylenediamine derivative is 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline salt. 9. The method for processing a silver halide color photographic material according to any one of Item 9. (11) The silver halide according to any one of claims 1 to 10, wherein the color photographic material is processed at a replenishment amount of 250 ml/m^2 or less during continuous processing. A method of processing color photographic materials. (12) A method for processing a silver halide color photographic material according to claim 11, wherein the color photographic material is processed at a replenishment amount of 200 ml/m^2 or less during continuous processing.