JPS6249350A - Processing of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable the rapid and stable processing of a photographic element by developing a silver halide color photographic sensitive material contg. a practical silver chlorobromide emulsion having 5-60mol% silver bromide content as the silver halide emulsion of the green- and red-sensitive silver halide emul sion layers with a specified color developing soln. at >=30 deg.C for <=150sec. CONSTITUTION:A photographic element contg. a practical silver chlorobromide emulsion having 5-60mol% silver bromide content as the silver halide emulsion of the green- and red-sensitive silver halide emulsion layers is developed with a color developing soln. contg. an N-hydroxyalkyl substituted-p-phenylenediamine deriv. at >=30 deg.C for <=150sec. Even when a reduced amount of a replenisher is used during the development with the color developing soln., the photographic element is not affected by a change in the concn. of bromide ions and can always maintain constant and proper photoggraphic performance for a long period. The resulting color forming dyes and the part not subjected to color development are not faded or discolored even after storage for a long period.

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 photographic elements). The present invention relates to a novel processing method that has less dependence on bromide ion concentration fluctuations and processing time dependence, does not impair rapidity, and can obtain dye images with excellent photomagnetochromism and high storage stability.
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 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 reduction of silver halide are eluted into the developer and accumulated. Additionally, components such as inhibitors contained in photographic elements are leached into the color developing solution and accumulated.

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 a color developing solution, development inhibiting substances accumulate as a result of developing a photographic element as described above, but the -1 color developing agent and benzyl alcohol are consumed or accumulated in the photographic element and taken out, reducing the concentration of these components. Therefore, in the development processing method in which a large number of photographic elements are subjected to continuous M1 processing using an automatic processor, etc., the components of the color developing solution are kept at a constant concentration in order to avoid changes in the development finish characteristics due to changes in the concentration of the components. A means is needed to keep it within 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 overflow liquid, a concentrated low replenishment method has been widely used, in which the replenisher is concentrated and refilled in small amounts, and another method is to add a regenerating agent to the overflow liquid and use it again as a replenisher. has also been proposed and put into practical use.

[Problem to be Solved by the Invention 1] 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 also becomes more susceptible to the effects of concentration due to evaporation, and the concentration of the fatigued M plant described above usually increases. For example, when the halogen ion concentration increases, the development reaction is suppressed, and the legs of the characteristic curve become more suppressed. 1, 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 evaporation and regeneration operations, and there are also differences in throughput, especially at the beginning of the week when the number of orders is high. The difference between high season and off-season and on weekends when the number of orders decreases is a maximum difference of 1:5, and the composition of the processing liquid is affected by evaporation and the difference in the amount of replenisher. There are drawbacks to being 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 problems are primarily due to changes in bromide ions, which are development inhibitors, such as reducing the amount of bromide that accumulates by reducing the amount of silver bromide in the photographic element, or reducing the amount of bromide ions that accumulate due to evaporation or replenishment. It has also been proposed to reduce fluctuations in the concentration of bromide ions due to errors in the amount (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-ethylz-N-β-methanesulfonamide ethylaniline, even if the developability was improved, the processing stability did not improve as much as expected, and the It is affected by bromide ion concentration.

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 approximately 8 minutes, which is the general processing time.The strong demand of the 1st generation is the above-mentioned low replenishment from an economical 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. The above-mentioned developing agents, which have traditionally been used as the most suitable agents for developing silver chlorobromide emulsions in particular, have low hydrophilicity, which slows down the penetration of color developing agents into photographic elements. Penetrants have been investigated, for example by adding benzyl alcohol to the color developer.
Methods of speeding up color development are widely used. but.

In this method, the color did not develop sufficiently unless the treatment was carried out at 33°C for at least 3 minutes.In addition, the 0 color developing solution had the disadvantage of being easily affected by the subtle bromide ion concentration. ) is also known, but if the pH is 10
If it exceeds 15, 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 the processing time becomes highly dependent. There was a problem that it could happen.

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. 3,719,482), 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 a Schiff salt (US Pat. No. 3,342,559).

Re+search Disclosure, 197
No. 8, No. 15159) is also known, but 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. There is.

Furthermore, when a 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 weaker, resulting in 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).

Photographic Proc by Mason
esSing Chemistry pages 103-107,
Focal Press, 1988), the fact of incorporating this compound into photographic elements is covered by British Patent No. 787.7.
However, in the technology described in the patent IJI document, halogenated silver for black and white is incorporated into a silver photographic light-sensitive material or a photographic element for reversal, and its purpose is to promote only black and white development. It is to do so, and also,
No. 2422 discloses that 3-pyrazolidones are incorporated into 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 an oxy-type organic split-off group 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;
No. 2,515,147, No. 2,498,903, No. 4,038, 075, No. 4,119,482, British Patent No. 1,430,998, No. 1,455,413
No. 53-15831, 55-62450, 55-82451, 55-62452, 5
No. 5-62453, Special Publication No. 51-12322, No. 55
Compounds described in No. 49728, etc. have been investigated, but most of them have insufficient accelerating effects, and compounds that exhibit high accelerating effects not only have the disadvantage of forming fog, but also This was not suitable as a method for improving 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, OL52,822,922, etc., and its function is to adsorb development inhibiting substances such as unnecessary halogen released during development and unnecessary leaving groups of DIR couplers and DAR couplers. However, it does not actively promote development, and its development promotion effect is small, and although it is effective against fluctuations in iodide ion concentration, the process is completely stable against fluctuations in bromide ion concentration. No effect was obtained.

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
, N-diethyl-p-phenylenediamine sulfate and 3-
Toalkyl-substituted color developing agents with low water solubility such as methyl-4-amino-N,N-diethylaniline hydrochloride have high development activity and can be rapidly developed, but the color-forming dye has low fading resistance after processing. Known to be undesirable. On the other hand, it is said that it has high developing activity and is preferable (US Patent No. 3
, No. 658.950, No. 3.658.525, etc.)
3-Methyl-4=amino-N-ethyl-N-β-methoxyethylaniline-p-)luenesulfonate does yield 1llllE, but bromide ion concentration stability cannot be obtained and the photo after treatment Significant yellow staining occurs in unexposed areas of the element, especially when processed for short periods of time.
It has been found that it cannot be used in iJ4 speed processing because it has the disadvantage that the color developing agent remains and causes rough staining.

On the other hand, 3-methyl-4-amino-N-ethyl-β-methanesulfonamide ethyl aniline sesulfate monohydride and 3
-Methyl-4-amino-N-β-hydroxyethylaniline sulfate is published by Photographic Association Science and Engineering Vol. 1.8. As seen in No. 3.5-June, 1884, P. 125-137,
It was said that there was not much difference in the half-wave potential indicating the oxidation-reduction potential, and that both had weak developing activity.

Therefore, the development activity for silver chlorobromide emulsions is substantial.

It is said that there are almost no color developing agents that have high storage stability for dye images, and generally 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline sulfate is used together with benzyl alcohol. It was used.

However, in this case, as mentioned above, it is easily affected by changes in the bromide ion concentration, and in concentrated low replenishment processing in which the amount of replenisher is reduced, another problem is an increase in the M product of other processing liquid components. There is.

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 in from the color developer by splashes from adjacent processing solutions in the processing machine, transport leaders, belts, hangers for hanging the film, etc. It will be done. 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 one-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 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 purpose 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 low replenishment amount using a single color developing solution, and to provide a color developing solution that can To provide a rapid and stable method for processing photographic elements in which uncolored areas do not fade or change color even after long-term storage.

Other objects of the invention will become apparent from the description below.

[Means for Solving the Problem] As a result of various studies to achieve the above-mentioned object of the present invention, the present inventor has developed a unique color development that is almost unaffected by the bromide ion concentration when developing a specific silver halide. Although they succeeded in finding the main drug, they encountered a problem in that the storage stability of the resulting color pigment decreased, so they further investigated ways to solve this 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, at least green-sensitive and red-sensitive silver halide emulsion layers can be used. A photographic element in which the silver halide emulsion in the emulsion layer is essentially a silver chlorobromide emulsion with a silver bromide content of 5 to 60 mol % is subjected to color development containing a tohydroxyalkyl-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 liquid.

The progress that led to the present invention will be explained below.

The inventor has discovered that when developing a photographic element using a particular silver halide, i.e., silver chlorobromide-based emulsion, the bromide ion concentration increases only when the color developing agent is a tohydroxyalkyl-substituted p-phenylenediamine derivative. We have found the surprising fact that the dye density obtained hardly decreases even when the amount 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 it has been used exclusively for the development of silver bromide emulsions, and it cannot be understood from the fermentation reduction potential or half-wave potential of general color developing agents, and there is a possibility that the development speed and coupling This was surprising because it could not have happened unless an optimal balance of speed was maintained.

However, the inventor encountered the following problem. It is rapid when using hydroxyalkyl-substituted -p-, phenylenediamine color developing agents, is insensitive to changes in bromide ion concentration, and can be developed especially under high bromide ion concentrations, so it can be refilled in continuous processing. Although it has the great advantage of being able to greatly reduce the amount of coloring and has extremely high processing stability, it has been found that it has the disadvantage that the storage stability of the resulting coloring dye, especially the ancestral color properties, is reduced. The storage stability of 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
We found that this problem occurs not because the storage stability of the dye itself is low, but because the single-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, the problem arises that if the conventional photographic element is used as it is, the developing time is insufficient and a sufficient photographic image cannot be obtained.Therefore, the present inventor has further studied and developed a method using the color developing agent of the present invention to remove bromide. In order to perform 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 silver bromide content of 5 to 60 mol%. The development rate is improved by processing a photographic element, which is a silver chlorobromide emulsion, with a developer containing an N-hydroxyalkyl-substituted-p-phenylenediamine derivative, and the photographic element can be rapidly developed in a range of 30° C. to 150 seconds. By carrying out color development, it was possible to achieve the above-mentioned object of the present invention without impairing the stability of the dye image.

N-hydroxyalkyl-substituted -p-
The fact that processing with a developer containing a phenylenediamine derivative improved development speed was unexpected and surprising.

In this specification, "substantially silver chlorobromide emulsion" or "substantially silver chlorobromide emulsion" may contain a trace amount of silver iodide in addition to silver chlorobromide; for example, 0.3 mol%
Hereinafter, it means that silver iodide may be contained more preferably in an amount of 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 light-sensitive emulsion layer of a photographic element processed according to the present invention comprises:
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 % - P Island In the present invention, each of the blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and red-sensitive silver halide emulsion layer is 2F.
f! ! In the present invention, the silver bromide content refers to the total silver halide contained in each of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer. If the silver bromide content, which refers to the total silver bromide content in each layer, exceeds 60 mol %, the development speed will be poor and the processing stability will be poor. In addition, the silver bromide content is 5 mol%
In the present invention, if the value is less than 0, the processing stability is inferior.
The silver bromide content of the green-sensitive and red-sensitive silver halide emulsion layers is preferably 20 to 55 mol%, more preferably 30 to 5 mol%.
It is 0 mol%.

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 0.20 to 0.55 #Lm, more preferably 0.30 to 0.50 p, rs. In terms of processing stability, the average particle size Q is preferably 55 #Lra or less, while in terms of sensitivity and prevention of magenta color turbidity, the average particle size is 0.
．． 20 p-ta or more is preferable.

The composition of the silver halide contained in the blue-sensitive silver halide emulsion layer of the present invention is not particularly limited, and may be any of silver bromide, silver chlorobromide, and silver chloroiodobromide, but silver chlorobromide is preferable. used.

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 0.1 to 2 mm.

More preferably 0.2 to 1JL11, particularly preferably 0
．． 25-0.8 lm.

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.

The coating silver amount in the photographic element of the present invention is preferably small, since there is no delay in development due to an increase in bromide and sufficient dye formation can be achieved even in a short time, and 0.3 to Ig is particularly preferred. The maximum effect is obtained at 8 g/m''.

The silver halide used in the Copy 1c elements of this invention may be polydisperse emulsions with average grain sizes distributed over a wide range, but 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 when the emulsion is observed using an electron microscope, and have uniform grain sizes.
And it has particle and 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 i, the value is 0.20 or less, preferably 0.15 or more -≦0.20 What is 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 60 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 light source chromaticity of the cyan dye will increase significantly, which is undesirable.The processing temperature is 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 higher, more preferably in the range of 8 to 13.

The developing agent effective in the present invention is a quaternary ammonium salt of a hydroxyalkyl-substituted -P-phenylenediamine 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 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Rz is a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms. is an alkyl group, R3 is an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, and A
is an alkyl group that has at least one hydroxyl group and may have a branch, and is more preferably ACH2. represents an alkyl group having 1 to 3 carbon atoms which may be optionally substituted, and at least one of R4, Rs, and R@ is a hydroxyl group or an alkyl group having a hydroxyl group.

nt, nz, R2 are each 0, 1.2 or 3,
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); Examples include 4-amino-3-methyl-
Examples include N-ditiruto(β-hydroxyethyl)-aniline salt and 4-amino-N-ethyl-N-(β-hydroxyethyl)-aniline salt.

Preferably, in the present invention, 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate hydrate [this is commercially available under the name CD-4, and In the color photography method of parts (for example, Eastman Kodak Co., Ltd. 041 method, Konishiroku Photo Industries Co., Ltd. C)
The NK-4 system (used for developing color negative films) has been found to be particularly effective.

Preferred hydroxyalkyl substitutions for use in the present invention
Examples of p-phenylenediamine derivatives include the following, but are not limited to these exemplified compounds. [Exemplary compounds] ll2 NF■2 112 H2 NI■2 ll2 N) I 2 Below margin (1) Hydrochloric acid, sulfuric acid, and P-)luenesulfonic acid salts of the compounds (8) to (8) are particularly preferred.

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

(7) and (8) are preferably used, especially No., (1
), (2) and (6) are preferably used. moreover,
In particular, No. (1) is preferably used in the present invention.Since the solubility of the color developing agent of the present invention in water is extremely high, the amount used is preferably in the range of 1 g to 100 g per treatment solution. , more preferably 38-30
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 Society Vol. 73, p. 3100 (195
It can be easily synthesized by the method described in 1).

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. The color developing agent and material that may be used in combination are typically those based on p-phenylenediamine, and the following are 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-amino-N-ethyl-N-β-methoxyethylaniline, 3-7cetamido 4-amino-N, N-dimethylaniline, N-ethyl-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, hydrochlorides, sulfites, p-toluenesulfone These are acid salts, phosphates, 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. 3100-3125 (1951).
The ones described above are also listed as representative ones. The amount of the color developing agent that may be used in combination is not particularly limited, but is preferably equal to or less than the same mole relative to the tohydroxyalkyl-substituted p-phenylenediamine derivative developing agent of the present invention.

The color developing solution of the present invention has a bromide ion concentration of 5 x 10-3.
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 and the color developer of the present invention, 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, in the present invention, the amount of replenishment can be reduced because it is less affected by the bromide ion concentration.

The bromide ion concentration is preferably lXl0-2 mol or more,
Particularly preferred is 1.5XlQ-2 moles or more.

If the bromide ion concentration is too high, development will be inhibited, so that the influence of the bromide ion concentration begins to appear, which is not preferable if it exceeds 6.times.10@-2 mol, but the chloride ion concentration has no effect.

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 14Ba when dry.
It is preferably at most t, more preferably at most 13 Bats, particularly preferably at most 12 Bats.

In the processing method of the photographic element 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 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 restrictions on the processing method for the photographic element of the present invention, and any processing method can be applied.For example,
Typical methods include 1 color development, followed by bleach-fixing and, if necessary, further washing and/or stabilization. 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, Method 1: The developed silver produced by color development is subjected to norogenation 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 bisulfite, flukali metal thiocyanate, alkali metal halide, benzyl alcohol,
Water softener.

A thickening agent, a development accelerator, etc. can also be optionally included.

Examples of additives other than the above that may be added to the color developer include bromides such as potassium bromide and sodium bromide, alkali iodide, 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.

For use in the bleaching solution or bleach-fixing solution in the bleaching process 1. Generally known bleaching agents include aminopolycarbonate or those prepared by coordinating metal ions such as iron, copper, copper, etc. with organic acids such as oxalic acid and citric acid. and above 7
Representative examples of minoboricarboxylic acid include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid glycol etherdiaminetetraacetic acidethylenediaminetetrapropionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acidpentasodium saltnitrilotriacetic acid sodium saltBleaching solution contains various additives along with 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. The bleach-fix solution may further contain halogen compounds, such as potassium bromide, and, as in the case of the above-mentioned bleach solutions, various other additives, such as p) 11 buffering agents, optical brighteners, etc. agent, antifoaming agent, surfactant.

Preservatives, chelating agents, stabilizers, organic solvents, etc. may be added or contained.

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.

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.

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. 2,533,472, No. 2,958,879, No. 3,125,448, No. 3,148,187,
3,177.078, 3,247,127, 3,260,601, 3.540.887, 3
．． No. 575.704, No. 3,653,905, No. 3,
No. 718,472, No. 4,071,312, No. 4,0
Examples include those described in No. 70,352.

These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use X+o−3 to 5×bo-mol,
More preferably, t x Ig-2 to 1×I〇-mol is used.

The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [1,0,01 planes to [1,1,1] planes 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. -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 to a predetermined size using an ammonia method, which has a fast growth rate.When growing silver halide grains, the PH, pAg, etc. in the reaction vessel may be adjusted. It is preferable to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains under controlled conditions, 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, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-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 chloroparadate (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 IQ-8 to 3
Optical sensitization may be achieved by adding 0 to 3 moles.

Various sensitizing dyes can be used, and each sensitizing dye can be used in various ways. ! Alternatively, two or more types can be used in combination. Examples of the sensitizing dyes 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. 929,0110, US Patent No. 2,231,858, US Patent No. 2,493,748, US Patent No. 2,503,776, No. 2,519,001, No. 2
, No. 912, 329, 3.85 [No. 1,959, 3.
, No. 872,897, No. 3,894,217, No. 4.
025.349, British Patent No. 4,048,572, British Patent No. 1,242.588, Japanese Patent Publication No. 44-14030, Japanese Patent Publication No. 52-24844, etc. Examples of sensitizing dyes that can be incorporated into silver halide emulsions include U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes and composite cyanine dyes as described in British Patent No. 2,945.763 and British Patent No. 505.979. Furthermore, sensitizing dyes used in red-sensitive silver halide emulsions include 1, for example, U.S. Pat.
, No. 234, No. 2,270,378, No. 2,442,
No. 710, No. 2,454,829, No. 2,778,2
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 60 and the like. Furthermore, U.S. Patent 2,213
, No. 995, No. 2,493,748, No. 2,519,
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 001 and West German Patent No. 929.060 can be advantageously used in all-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. 54-6011
No. 8, No. 58-153926, No. 59-116646
No. 59-116647 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, No. 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.

Further, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication No. 44-32°753;
No. 6-11627, JP-A-57-1483, and regarding merocyanine, for example, JP-B No. 48-3840.
No. 8, No. 48-41204, No. 50-40662,
JP 56-25728, JP 58-10753, JP 58-91445, JP 59-116645, JP 50
-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 containing, for example, methyl alcohol, ethyl alcohol, acetone, dimethylform 7mide, or a fluorinated alcohol as described in Japanese Patent Publication No. 40659/1983 is prepared in advance. It is used by dissolving it in a hydrophilic organic solvent such as

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.

Each of the silver halide emulsion layers according to the present invention can contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

As the above-mentioned couplers that can be used in the present invention, various yellow couplers, magenta couplers and cyan couplers can be used without particular limitation. These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and in combination with these couplers, it is also possible to use diffusible dye-releasing type couplers.

The yellow cabbage contains an open-chain ketomethylene compound and an active site called a two-equivalent coupler.
〇-aryl substituted coupler, active point -〇-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound lead substituted coupler and active point succinimide compound substituted coupler, active point fluorine substituted coupler, active point chlorine or Bromine-substituted coupler, active point -o
-Sulfonyl substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Patent No. 2,875.057, U.S. Pat.
3.551,155, 3,582,322, 3,725,072, 3.891.445, West German Patent No. 1,547,888, West German Application Publication No. 2,219,
No. 917, No. 2,281,381, No. 2,414.0
No. 06, British Patent No. 1,425,020, Special Publication No. 1973-
No. 10783, JP-A-47-26133, JP-A No. 48-7
No. 3147, No. 51-102636, No. 50-634
No. 1, No. 50-123342, No. 50-130442
No. 51-21827, No. 50-87650, No. 52-82424, No. 52-115219, No. 58
-95346 etc. can be mentioned.

Examples of magenta couplers used in the present invention include pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indacylon compounds. 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 include U.S. Pat. Nos. 2,600,788 and 2,983.
, No. 608, No. 3.0f12,853, No. 3,127
, No. 289, No. 3,311.476, No. 3,419,
No. 391, No. 3,519,429, No. 3.558, 3
No. 19, No. 3,582,322, No. 3,815,50
No. 6.

No. 3,834,908, No. 3,891,445, West German Patent No. 1,810.484, West German Patent Application (OLS)
2,408,13 [No. 15, 2,417,945
No. 2,418,959, No. 2,424.467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 20826/1982, No. 52-58922, No. 49-129538, No. 49-74027 , No. 50-60233, No. 52-
No. 42121, No. 49-74028, No. 50-602
Examples include those described in No. 33, No. 51-26541, No. 53-55122, and Japanese Patent Application No. 110943/1983.

Furthermore, useful cyan couplers used in the present invention include, for example, phenolic 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. Pat.
, No. 434,272, No. 2,474,293, No. 2,
No. 521,908, No. 2,895,828, No. 3,0
No. 34,892, No. 3,311,476, No. 3,45
8.315, 3,478,583, 3,583
, No. 971, No. 3,591,383, No. 3,787,
No. 411, No. 3,772,002.

3.933.494, 4,004,929, West German patent application (OLS) 2,414,830, 2
．． No. 454.329, JP-A-48-59838, No. 5
No. i-26034.

No. 48-5055, No. 51-146827.

No. 52-69624, No. 52-90932, No. 58
-95346, Japanese Patent Publication No. 49-11572, and the like.

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

The above-mentioned coupler that can be used in the present invention may be added to the photographic constituent layer of the present invention by any conventional method, and the amount of the above-mentioned coupler added is not limited, but I
Q-3 to 5 mol is preferred, more preferably IXIG-
It is 2 to 5 x 10 - crows.

In addition to the above, the photographic elements of the present invention may contain various photographic additives, such as antifoggants, stabilizers, ultraviolet absorbers, and color stain prevention agents as described in Research Disclosure No. 17843. 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, hydrophilic colloids used to prepare the emulsion include gelatin.

Derivatives of gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinylimidazole, polyacrylamide, etc. Any synthesis of copolymers, wood-philic polymers, etc. 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 also be used, and these supports are appropriately selected depending on the intended use of the photographic element.

Various coating methods such as dipping 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. Also, U.S. Patent No. 2,781
It is also possible to use a simultaneous coating method of two or more layers by the method described in , No. 791 and No. 2,941.898.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily.For example, in the case of paper 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, The arrangement of red-sensitive silver halide emulsion layers is preferred, and each of these light-sensitive 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 protective layer, and an antihalation layer can be used in appropriate combinations as photographic constituent layers. In these constituent layers, wood-philic colloids that can be used in the emulsion layer as described above can be similarly used as a binder, and can also be contained in the emulsion layer as described above. Various photographic additives can be included.

[Effect of the invention 1 According to the present invention, there is no shadow of change in bromide ion concentration even when processing is performed with a low replenishment amount using a single color developer! Rapid and stable processing of photographic elements that can always maintain constant appropriate photographic performance over a long period of time without causing any damage, and that the resulting colored pigments and uncolored areas do not fade or change color even after long-term storage. We can provide a method.

[Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 Samples Nos. 1 to 12 were prepared by sequentially coating the following layers on a paper support laminated with polyethylene from the support side.

Layer 1 - 1.2g/m gelatin, 0.27g
/rn' (in terms of silver, the same applies hereinafter) blue-sensitive silver halide gelatin emulsion (silver halide Mi composition and average grain size are shown in Table 1), 0-. 0.60 g/m' of yellow coupler (Y-
A blue-sensitive silver halide emulsion layer containing 1).

Layer 2 * * a 0.70 g/m″ gelatin,
10+sg/rn' anti-irradiation dye (A
I-1), an intermediate layer consisting of (A I-2) of 5+sg/go.

Layer 3 - 1.25g/gelatin, 0.28g/
green-sensitive silver halide gelatin emulsion (silver halide composition and average grain size are shown in Table 1), 0.3 (Ig/
0.82 g/ln' dissolved in dioctyl 7 tallate
Green-sensitive silver halide emulsion layer containing rrf magenta coupler (M-1).

Layer 4...* 1.2g/ba gelatin, IO, 8g/
An intermediate layer consisting of a green UV absorber (UV-1).

Layer 5: 1.4 g/g of gelatin, 0.20 g/g of red-sensitive silver halide gelatin emulsion (silver halide composition and average grain size are shown in Table 1), 0.20 g/rrr'
0.45 g/rn' dissolved in dioctyl phthalate of
A red-sensitive silver halide emulsion layer containing a cyan coupler (C-1).

Layer 6---0.50 g/ln' gelatin, 10.
Protective layer consisting of 3 g/m'' of UV absorber (UV-1).

Layer 7: Protective layer containing 0.90 g/m'' of 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.

Below margin Table 1 Zero l blue-sensitive silver halide emulsion layer, the same applies hereinafter.

Underneath: green-sensitive silver halide emulsion layer, the same hereinafter.

Book 3 Red-sensitive silver halide emulsion layer, same hereinafter.

t t (AI-1) (AI-2) (UV-1) 0,,H2(t) In addition, as a hardening agent, 2.4-dichloro-6-hydroxy-S-triazine sodium was added to the layer 2.4. and during 6,
Each was added in an amount of 0.02 g per Ig of gelatin.

Each of samples Nos. 1 to 12 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 60 seconds Drying 60-60°C 120 seconds The composition of each processing solution is as follows.

[Color developer] Pure water 600ml Benzyl alcohol 15ml Hydroxyamine sulfate 2.0g Potassium bromide
0.6g sodium chloride
1.0g potassium sulfite
2.0g triethanolamine
2.0g color developing agent (as shown in Table 1) 0.0
23 moles! -Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5 m magnesium chloride 0.3 g potassium carbonate 328 Kayco l I-
PK-Conc (fluorescent brightener, manufactured by Shinnichi Kako Co., Ltd.) Add 2mM pure water to make it 141, and p with 20% potassium hydroxide or 10% dilute sulfuric acid.
Adjust to u=+o, t.

[Bleach-fix solution] Pure water 550 ml Iron ethylenediaminetetraacetate (m) Ammonium salt 85 g Ammonium thiosulfate (70% aqueous solution) 85 g Sodium bisulfite IOg Sodium metabisulfite
2g ethylenediaminetetraacetic acid-disodium 2
Add 0 g of pure water to make one sentence, and adjust to pl = 7.0 with aqueous ammonia or dilute sulfuric acid.

Separately, the potassium bromide concentration of the color developer is 0.58/
The same sample No. 1 as above was prepared using a color developing solution with the only difference that l was 1.5 g/i and 3.5 g/cross.
Each of 12 to 12 was developed.

Sensitometry was performed on each sample obtained by a conventional method. Table 2 shows the change in concentration when the potassium bromide concentration was varied at an exposure dose of 1.0 for each sample when the potassium bromide concentration was 0.5 g/fL. Here, ΔD in Table 2 is the difference between the concentration when potassium bromide is 0.5 g/l and the concentration when potassium bromide is 3.5 g/l, and indicates the photographic performance when the potassium bromide concentration changes. represents the magnitude of the fluctuation.

Margin Table 2 Comparative color developing agent (CD-33 (CD-6)) As is clear from the results in Table 2, in the case of the color developing agent of the present invention, the halogen in the green-sensitive and red-sensitive silver halide emulsion layers is Sample N in which the silver bromide content of silver bromide grains is 60 mol% or more
o, 1 to 5, the silver bromide content of the silver halide grains in the green-sensitive and red-sensitive silver halide emulsion layers of the present invention is 5 to 6.
Samples No. 096 to 12 containing 0 mol% show no significant change in color density even when the bromide ion concentration in the color developing solution changes from 0.5 g to 3.5 g, indicating high processing stability. When the developing agent is CD~3, the silver bromide content of the silver halide grains in the green-sensitive and red-sensitive silver halide emulsion layers is B.

Compared to samples Nos. 1 to 5, which have a silver bromide content of 5 to 60 mol % in the silver halide grains of the green-sensitive and red-sensitive silver halide emulsion layers, samples Nos. 46 to 12 have a color density of 5 to 60 mol %. Although the change is small, it can be seen that the improvement is small compared to the color developing agent of the present invention.

In the present invention, the average grain size of blue-sensitive silver halide is 0.7.
p, tx sample No. 8~8 and 0.5gm No. 9~
Comparing No. 12, the average grain size of blue-sensitive silver halide is 0.
．． It can be seen that the sample of No. 5 and No. 1 has higher processing stability and is more preferable.

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 Sample No. 9 of Example 1 was exposed and developed in the same manner as in Example 1 using the same processing solution. The 0 color development times that were prepared and subjected to processing were varied as shown in Table 3. The treatment temperature was 38°C.

The obtained sample was stored under xenon lab irradiation, and changes in cyan concentration were measured. That is, at each processing time aIN
For each case, when the initial sample density of 1.0 when CD-3 was used as the color developing agent deteriorated by about 0.3, the decrease in density in the same concentration range of the sample treated with another color developer was measured and shown in the table. Shown in 3. At this time, the yellow stain density of the unexposed area of the same sample was measured and similarly shown in Table S.

As is clear from the results in Table 3, when a single color developer uses GO-3 or CD-8 as a color developing agent, there is no significant difference in the fading rate no matter how many seconds the color development time is. Among them, it can be seen that the color fading is greater in the case of co-e than in GO-3. This also applies to the yellow stain density (Dmin) of the unexposed area.

On the other hand, in the case of the color developing agent exemplified compound (1) of the present invention, when the color development processing time is 160 seconds or more, the color fading is large and the storage stability is extremely low. ).

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 preferable results than when using the above-mentioned CD-3. This is surprising considering that it has traditionally been said that the structure of color-forming dyes is closely related to the stability of the dye, and it is predicted that the residual content of the color-forming developing agent in one area may also be closely related. be done.

Example 3 Samples No. 4 and No. 9 of Example 1 were used, and the same processing solution as in Example 1 was used to evaluate the rapidity.

Color development time is Go, 70.8G, 90,100.
110°120, 130.140, 150.160, 1
70, 18o.

190, 200. 210, 220, 230, 240,
The processing time required to obtain a maximum density of 90% of the maximum density of yellow when color development is performed for 600 seconds at 300, 420, 600 (seconds) is shown on the table.

Table 4 As is clear from the results in Table 4, when the color developing agent of the present invention is used, rapidity can be obtained, but in the case of Sample No. 4 using silver halide grains other than the present invention, Example As discussed in Section 2, it is not possible to obtain a development processing time that satisfies image preservability, but in sample No. 9 using the silver halide grains of the present invention, sufficient photographic performance was obtained in 150 seconds.
It can be seen that the image storage stability is also sufficiently satisfactory.

This result indicates that the silver halide composition of the green-sensitive and red-sensitive silver halide emulsions has an influence on the developability of the blue-sensitive silver halide emulsion layer.
There was something that should have been done that was unimaginable using conventional wisdom.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Agent
Patent attorney Nobuaki Sakaguchi (and 1 other person) Procedural entry (on his own initiative) September 16, 1985 Patent Application No. 161436/1980 2 Name of the invention Processing method for silver halide color photographic light-sensitive materials 3 Correction Applicant name (127) Konishiroku Photo Industry Co., Ltd. 4 Agent 160 Address 2nd Building, 5th floor, 7-10-11 Nishi-Shinjuku, Shinjuku-ku, Tokyo (03) 361- 0055 (Main) FAX361-
0103 Name (7321) Patent attorney 0Akira Sakaguchi (and 1 other person) 5 Date of amendment order Spontaneous 6 Number of inventions increased by amendment Contents of amendment (Special Q! No. 1614:1688) About the specification Correct as shown below.

l On page 27, line 13, the name ``CD-4'' is corrected to the name ``CD-4''.

2. On page 40, line 7, the phrase "layered structure" is corrected to "layered or lamellar structure."

3. On page 47, lines 18-19, the phrase "open-chain ketomethylene compound" is corrected to "closed-chain ketomethylene compound."

4 On page 60, line 17, “Potassium bromide [1.6g
"J" should be corrected to "potassium bromide 0.5 gJ.

5. On page 66, line 13, the text "rxenon lab J" is corrected to "xenon lamp."

that's all

Claims (11)

[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 essentially a silver chlorobromide emulsion containing 0 mol % of N-hydroxyalkyl-substituted -p
- A method for processing a silver halide color photographic light-sensitive material, which comprises developing at 30°C or higher and 150 seconds or less using a color developing solution containing a phenylenediamine derivative. (2) A patent claim characterized in that the silver halide emulsion of at least the green-sensitive and red-sensitive silver halide emulsion layers is substantially a silver chlorobromide emulsion with a silver bromide content of 20 to 55 mol%. A method for processing a silver halide color photographic material according to item 1. (3) The silver halide color according to claim 1 or 2, wherein the average grain size of the silver halide in the blue-sensitive silver halide emulsion layer is 0.20 to 0.55 μm. Method of processing photographic materials. (4) The silver halide color according to any one of claims 1 to 3, 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. (5) 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 4. (6) Claim 5, 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 . (7) A method for processing a silver halide color photographic light-sensitive material according to claim 5, characterized in that processing is performed with a color developing solution containing 1.5 x 10^-^2 moles or more of bromide. (8) The method for processing a silver halide color photographic material according to claim 4, wherein 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-ethyl-
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 N-β-hydroxyethylaniline salt is used. (10) The silver halide according to any one of claims 1 to 9, 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. (11) A 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.