JPS627050A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To permit appropriate photographic performances to be maintained for a long period, unaffected by Br ion concentration by processing a photographic element having at least one silver chlorobromide photosensitive emulsion layer and containing a specified compound with a p-phenylene type developing solution in a short time. CONSTITUTION:The photographic element formed on a support has blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers, and at least one of the photosensitive silver halide emulsion layers has a silver chlorobromide emulsion, and said element contains the compound represented by the formula shown on the right (each of R1, R2 is optionally substituted alkyl). This element is processed at >=30 deg.C within 150sec with a color developing solution containing an N- hydroxyalkylated-p-phenylenediamine derivative, thus permitting always constant appropriate photographic performances to be maintained for a long period, unaffected by the change of Br concentration even if it is processed with said developing solution in a small replenishing rate, and the developed and nondeveloped color arts not to suffer from fading and discoloring even for long storage, and the photographic element to be processed stably and rapidly by this processing method.

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 new processing method that has less dependence on bromide ion concentration fluctuations and less dependence on processing time, does not impair speed, and can obtain dye images with excellent original color properties and long shelf life.
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 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 regenerating agent to the overflow liquid and use it again as a replenisher. Methods have also 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, and the concentration due to evaporation will also be affected. For example, when the halogen ion concentration increases, the development reaction is suppressed, and the legs of the characteristic curve are further suppressed, resulting in high contrast. This results in the problem of deterioration. To avoid this, overflow the liquid from the ion exchange resin or electrolyte.

A method has been proposed in which halogen ions are removed by gas dialysis, a regenerating agent is added to compensate for the deficient components generated during development and deficient components lost during regeneration processing, and the solution is regenerated and used again as a replenisher.

These regeneration and concentrated low replenishment methods using ion-exchange resins and electrodialysis are susceptible to fluctuations in bromide ion concentration due to 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 the fluctuation 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 developing solution using amino-N-ethyl-N-β-methanesulfonamide ethylaniline, improving the developability makes it easier to absorb the effects of fluctuations in the bromide ion concentration in the developer, resulting in stable processing. The result is the opposite of what one would expect: sex would be impaired.

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

Conventionally, in color paper processing consisting essentially of a silver chlorobromide emulsion, one 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 processing and stabilizing processing 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, have low hydrophilicity, so that the penetration of color developing agents into photographic elements is slow. Penetrants have been investigated, such as 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 3 minutes or more, and it also had the disadvantage that it was easily affected by the subtle bromide ion concentration.The pH of the 0 color developing solution There is also a known method to raise the pH, but if the pH is 10.
If the value exceeds 5, the oxidation of the color developing agent becomes extremely rapid, and since 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 one-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 a Schiff salt (US Pat. No. 3,342,55θ).

Research 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 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.

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

Author: Photographic Process
Ssing Chemistry pages 103-107, F
ocal Press, 196B), the fact of incorporating this compound into photographic elements is covered by British Patent No. 787.704.
However, in the technology described in the above-mentioned patent specification, silver halide is incorporated into a black and white photographic material or a reversal photographic element, and its purpose is to promote only black and white development. Furthermore, in JP-A-53-52422, 3-pyrazolidone is used 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 for speeding up color development processes by stabilizing them with low replenishment processes.

Further, as a conventionally known method of accelerating color development using an accelerator, US Pat. No. 2,850,970;
No. 2,515,147, No. 2,4138.903,
4,038.075, 4,119,482, British Patent No. 1,430,998, 1,455,413, JP 53-15831, JP 55-62450,
No. 55-62451, No. 55-62452, No. 55
-62453, Special Publication No. 51-12322, 55-
Compounds described in No. 49728 etc. were investigated, but
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, OLS No. 2,822,922, etc., and its function is to adsorb development inhibiting substances such as unnecessary halogens released during development and unnecessary leaving groups of DIR couplers and DAR couplers. However, it does not actively promote development, and its development promotion effect is not only small.

Although it was effective against fluctuations in iodide ion concentration, no treatment stabilization effect was obtained against fluctuations in bromide ion concentration.

On the other hand, the speed of color development varies depending on the type of paraphenylenediamine derivative used and is said to depend on the redox potential. Among these color developing agents, N
, 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.). -Gp-) 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. However, it was found that the color developing agent remained behind, causing rough stains, and that it could not be used in rapid processing.

On the other hand, 3-methyl-4-amino-N-ethyl-β-methanesulfonamide ethylaniline sesquisulfate monohydrade and 3
-Methyl-4-amino-N-β-hydroxyethylaniline sulfate, etc. Photographic Science and Engineering Vol. 1.8. No., March 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, it is said that there are almost no color developing agents that have high developing activity for silver chlorobromide emulsions and excellent storage stability of dye images, and generally, 3-methyl-4-amino-ethyl-N-β- Methanesulfonamidoethylaniline sulfate was used 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. Contamination with other processing solutions is caused by so-called pack contamination, in which processing solution components immediately after development are brought into 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 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 j 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 method 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 hole emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, at least the IM light-sensitive emulsion layer the silver halide emulsion is essentially a silver chlorobromide emulsion;
and 20 mg/r of the compound represented by the following general formula (I)
It has been found that the above object can be achieved by processing a photographic element containing more than RF using a color developing solution containing a -hydroxyalkyl-substituted-p-phenylenediamine derivative at a temperature of 30° C. or more and 150 seconds or less. .

General formula [I] ■ R1-0-C-CHz R2-0-C-CH-5Oz Ha In the formula, R1 and R2 may be the same or different, and each represents an alkyl group that may have a substituent. represent.

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

The present inventor has discovered that a specific silver halide, namely silver chlorobromide-based (
In particular, when developing photographic elements using emulsions with a silver bromide content of 90 mol % or less, the bromide ion concentration increases only when the color developing agent is an N-hydroxyalkyl-substituted p-phenylenediamine derivative. We have found the surprising fact that the dye density obtained by this method is almost unchanged.

The above characteristics of this color developing agent include 0.5 mol% of silver iodide.
This cannot be achieved with a photographic element using a silver iodobromide emulsion containing substantially all of the above, and is not expected since this type of color developing agent has traditionally been used exclusively for the development of silver iodobromide emulsions. In particular, if the silver bromide content is 9.
The fact that the development speed is not slowed down even with large increases in bromide ion concentration during the development of photographic elements using substantive silver chlorobromide emulsions of less than 0 mole percent is unexpected, and the general color development This is surprising because it cannot be understood from the oxidation-reduction potential or half-wave potential of the developing agent, and it probably cannot occur unless an optimal balance between development speed and coupling speed is maintained.

However, the inventor encountered the following problem. It is rapid when using N-hydroxyalkyl-substituted-p-phenylenediamine color developing agents, is insensitive to changes in bromide ion concentration, and can be developed especially at 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).

As a result of further efforts by the present inventor to solve this problem,
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 perform low replenishment processing without being affected by an increase in ion concentration, the silver halide emulsion in at least one layer, preferably all light-sensitive emulsion layers, is substantially a silver chlorobromide emulsion, and the above-mentioned general The compound represented by formula [I] (hereinafter referred to as the compound of the present invention) at 20 mg/r11
The photographic element containing f or more is hydroxyalkyl-substituted.
Development speed was improved by treatment with a developer containing a p-phenylenediamine derivative, and the photographic element was heated at 30°C.
It was only through rapid color development within the range of 150 seconds or less that the object of the present invention could be successfully achieved without impairing the stability of the dye image.

It has been known that photographic properties such as development speed change depending on the type of surfactant, but compared to normal processing, N
-When developing using a color developing solution containing a hydroxyalkyl M-substituted p-phenylenediamine derivative,
The present inventor has found that the influence of this surfactant is large (that is, the dependence becomes large), and especially when the compound of the present invention is used, the development speed becomes large and even more rapid processing becomes possible. It is something.

In this specification, "substantially silver chlorobromide emulsion" to "
The term "substantially silver chlorobromide emulsion" means that it may contain a trace amount of silver iodide in addition to silver chlorobromide. 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 described in further detail below.

The light-sensitive emulsion layer of a photographic element processed according to the present invention comprises:
At least one layer is substantially a silver chlorobromide emulsion (hereinafter referred to as
The silver chlorobromide emulsion of the present invention may be formed from the silver chlorobromide emulsion of the present invention, but it is preferable that all of the photosensitive emulsion layers consist of the silver chlorobromide emulsion of the present invention.

As described above, the photographic element of the present invention may have at least one light-sensitive emulsion layer containing the silver chlorobromide of the present invention, but at least a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer. It is preferable that the layer contains the silver chlorobromide emulsion of the present invention, and more preferably, the green-sensitive silver halide emulsion layer, the red-sensitive silver halide emulsion layer, and the blue-sensitive silver halide emulsion layer each contain the silver chlorobromide emulsion of the present invention. Contains an emulsion.

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 2M
In the present invention, the silver bromide content refers to the total green-sensitive silver halide emulsion layer, the total blue-sensitive silver halide emulsion layer, and the total red-sensitive silver halide emulsion layer. The silver bromide content is preferably 90 mol% or less in terms of processing stability and prevention of magenta color turbidity, which refers to the total silver bromide content of each layer in the total silver halide contained in the silver halide. In particular, the silver bromide content is preferably 90 mol% or less, and from the viewpoint of processing stability, it is preferable that the silver bromide content is no less than 5 mol%. The silver bromide content of the photosensitive emulsion layer is preferably 20 to 55 mol%, more preferably 30 to 5 mol%.
It is 0 mol%.

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 may be any of silver bromide, silver chlorobromide, and silver chloroiobromide. .

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 0.20-0.55 pm, more preferably 0.30-0.501 Lm. In terms of processing stability, the average particle size is 0.55. - preferred, on the other hand.

The average particle size is 0.2 in terms of sensitivity and prevention of magenta color turbidity.
0 ru ■ or more is better.

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 layer or 2 layers, more preferably 0.1 layer or 2 layers.
2 to IIL11, particularly preferably 0°25 to 0.81L
It is m.

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 period of time, from 0.3 to Ig/m
2, especially when the amount is 0.4 to 0.8 g/m2, the maximum effect can be obtained.

The silver halide used in the photographic elements of this invention may be a polydisperse emulsion 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 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 f, the value is 0.15 or less.

The particle size herein has the same meaning as the particle size described above regarding the average particle size.

Next, the compound of the present invention represented by the above general formula (1) will be explained.

-M In formula [I], examples of the alkyl group include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, Straight chain or splitting alkyl groups having 4 to 19 carbon atoms, such as hexadecyl, heptadecyl, octadecyl, and nonadecyl groups, are preferred, and straight chain or splitting alkyl groups having 5 to 12 carbon atoms are particularly preferred. .

Examples of substituents for the above alkyl group include an alkoxy group,
Examples include a halogen atom, a cyano group, and a hydroxyl group.

Representative examples of the compounds of the present invention include the following.

The following margin [Example compounds] j (n) 0s) ts7-0-Cney CH2 (ko) Cl
6H33-0-C-CI(2UH3-(UH2 bar(,
;H-CH2-0-C-CH-9O3Na Below margin These compounds of the present invention are Zh, Pr1kl, Khi
m, Volume 41 (19138) 230? It can be easily synthesized based on the description on the page.

The compound of the present invention is used at 20 mg/m'' or more,
More preferably 30mg/rn” to 200mg/
It is used within the range of rn'.

The compound of the present invention may be used in any of the photographic constituent layers (including not only silver halide emulsion layers but also all hydrophilic colloid layers such as intermediate layers, protective layers, and subbing layers). ,
Preferably, it is contained in the blue-sensitive silver halide emulsion layer and/or its adjacent layer.

The method or timing of adding the compound of the present invention to the photographic constituent layer is arbitrary; it may be added to the photographic constituent layer coating solution also as a coating aid, or, for example, it may be added to the blue-sensitive silver halide emulsion layer. In this case, the yellow coupler may be used as an emulsifier when dispersing with a high boiling point solvent.

The compounds of the invention may be used in combination with other surfactants.

Surfactants that may be used in combination may be anionic, cationic, amphoteric, or nonionic, and examples of anionic surfactants include alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates,
Alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-aziroot alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Those containing an acidic group such as a carboxy group, a sulfo group, a phosphor group, a sulfuric acid ester group, or a phosphoric acid ester group are preferable. Examples of cationic surfactants include alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. etc. are preferred.

Preferred examples of the amphoteric surfactant include amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, and amine oxides.

Examples of nonionic surfactants include saponin (steroid type), alkylene oxide derivatives (such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene Glycol alkyl ethers, polyalkylene glycol alkyl amines or amides, polyethylene oxy F adducts of silicones), glycidol derivatives (e.g. alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, Alkyl esters and the like are preferred.

The amount of the surfactant that may be used in combination is preferably equal to or less than the amount of the compound of the present invention.

The color development process in the present invention is carried out at 30°C or higher and at 150°C.
It is carried out for 120 seconds or less, preferably at 33°C or more.
The treatment time is preferably 90 seconds or less at 35° C. or higher, and preferably 90 seconds or less at 30° C. or higher. If the treatment is performed at 30° C. or higher and 150 seconds or longer, the storage stability of the dye deteriorates.

In particular, the processing time is more important than the processing temperature, and if it exceeds 150 seconds, the cyan dye's chromaticity will increase significantly, which is undesirable. 30℃
As mentioned above, if it is 50℃ or less, the higher the temperature is, the shorter the treatment time becomes possible, and it is rather preferable.
The temperature is 8°C or lower, most preferably 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.

The developing agent effective in the present invention is a quaternary ammonium salt of an N-hydroxyalkyl-substituted p-phenylenediamine compound, particularly one that can be represented by the following general formula.

In the formula, 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 R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R2 is an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, and A is an alkyl group having at least one hydroxyl group and which may have a branch. R4, R5, and R6 each represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms that may have a hydroxyl group, and at least one of R4, R5, and RG is One is a hydroxyl group or an alkyl group having a hydroxyl group.

nl, R2, n'J are each 0.1.2 or 3, and HX is hydrochloric acid, sulfuric acid, p-)luenesulfonic acid,
Represents nitric acid or phosphoric acid.

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

Preferably, in the present invention, doamino-3-methyltoethyl (β-hydroxyethyl)-aniline sulfate hydrate [which is commercially available under the name CD-4 and is used in most color photographic systems] is used. (For example, Eastman Kodak Co., Ltd. 041 method, Konishiroku Photo Industries Co., Ltd. CNK-
(To develop color negative film such as 4 method)
was found to be particularly effective.

Preferred hydroxyalkyl substitutions for use in the present invention
The p-phenylenediamine derivatives include the following, but are not limited to these exemplified compounds.

[Exemplary compounds]

N.H.

NH2 NH2 N.H.

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. and (1).

(2) and (8) are preferably used. Furthermore, particularly No. (1), the solubility of the color developing agent of the present invention, which is preferably used in the present invention, in water is extremely high, so the amount used is within the range of 1 g to 100 g per 1 processing solution. is preferable, more preferably 3 g to 3
Used in the range of 0g.

These tohydroxyalkyl-substituted p-phenylenediamine derivatives of the present invention are described in the Journal of the American Chemical Society, Vol. 73, p. 3100 (1951).
It can be easily synthesized by the method described in 2010).

It goes without saying that other color developing agents can be used in combination with the N-hydroxyalkyl-substituted p-phenylenediamine derivative developing agent according to the present invention. A typical color developing agent that may be used in combination is a p-phenylenediamine type, 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-β-methoxyethylaniline, 3-7cetamido-4-amino-N,N-dimethylaniline, toethyl-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4 -Aminoaniline, toethylate β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and salts thereof such as sulfur salts, hydrochlorides, sulfites, p-)luenesulfonates, phosphates etc.

Furthermore, for example, JP-A-48-64932, JP-A-50-1
No. 31526, No. 51-95849, and Bent et al.'s 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 at most the same molar amount as the color developing agent of the present invention.

The color developing solution of the present invention has a bromide ion concentration of 5XIO-3.
In the present invention, a high bromide ion concentration is preferable because it reduces the amount of replenishment.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, the amount of replenishment can be lowered since the uninvented method is less affected by the bromide ion concentration.

The bromide ion concentration is preferably 1 x 10-2 mol or more,
Particularly preferably, it is 1.5X+o-2 mol or more, and if the bromide ion concentration is too high, development will be suppressed, so it is not preferable to have a bromide ion concentration of 6x10-2 mol or more, where the influence of the bromide ion concentration starts to appear. It does not affect.

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. In the present specification, it has the same meaning as not only the photosensitive emulsion layer, but also all the wood-loving colloid layers on the side coated with the photosensitive emulsion layer, such as intermediate layers, overcoat layers, and undercoat layers. ) The thickness of the gold film is 14g when dry.
It is preferably at most 13 gm, more preferably at most 13 gm, particularly preferably at most 12 gm.

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 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 how to do stable processing:
Or preduration, neutralization, color development, stop fixing, and water washing.

Method of bleaching, fixing, washing with water, post hardening, washing with water, color development, washing with water, supplementary color development, stopping, bleaching, fixing, washing with water,
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,
A water stopper, a thickening agent, a development accelerator, and the like may optionally be 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.

As bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process, 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 are generally known. There is. Representative examples of the above-mentioned 7-minopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylene diaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid glycol ether diaminetetraacetic acidethylenediaminetetrapropionateethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acidpentansodium saltnitrilotriacetic acid sodium saltBleaching solutions can be used with various bleaching agents as mentioned above. It may contain additives, and 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 also contain a halogen compound, such as potassium bromide, and, as in the case of the bleach solution described above, various other additives, such as pHTL buffer agents, optical brighteners, Adding antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc.
It may be included.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned.

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, 58-1346,
.

3412jl/M58-1863□Tsewa,i45
A stabilization treatment as an alternative to washing may be performed as shown in No. 8-2709 and No. 59-89288.

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. 1309, No. 1,277.429, JP-A No. 1977-8
No. 5130, No. 49-99620, No. 49-1144
No. 20, No. 49-129537, No. 52-10811
No. 5, No. 59-25845, No. 59-111640, No. 59-111641, U.S. Patent No. 2.274,78
No. 2, No. 2,533,472, No. 2,958,879
No. 3,125,448, No. 3,148,187, No. 3,177.078, No. 3,247,127,
No. 3,260,901, No. 3,540.887, No. 3,575,704, No. 3,853,905, No. 3
, No. 718,472, No. 4,071,312, No. 4,
Examples include those described in No. 070,352.

It is generally preferable to use these AI dyes in an amount of 2X+o@-3 to 5X+o@-@mol, more preferably 1.times.10@-2 to 1.times.10@-mol, per mol of silver in the emulsion layer.

The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [1,0,0] planes to [1,1,11 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.
9-170070) 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.

For example, the seed particles are made by an acidic method, and the growth rate bzyy-e=7 is determined by method 9 to 3″k/predetermined growth rate.
p) I, p in the reaction vessel when growing silver halide grains may be used.
jlg etc., for example, JP-A-54-485
It is preferable to sequentially and simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains as described in No. 21.

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 include: activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, dicatalyzed thio Urea, 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 a suitable sensitizing dye in an amount of 5 x 10-8 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 0 to 3 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. 929,090, 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. 3.858,959, No. 3,87
No. 2,897, No. 3,894,217, No. 4.025
．． No. 349, No. 4,048,572, British patents 1 and 2
No. 42.588, Special Publication No. 44-14030, No. 52-
Examples include those described in No. 24844. 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. 505,979, and the like. Further, as a sensitizing dye used in a red-sensitive silver halide emulsion, 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. 2,454,829, No. 2,778,290, 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. 929.090 and the like 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. 54-9011
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, 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, Japanese Unexamined Patent Publication No. 1483/1983, and Japanese Patent Publication No. 38408/1983 regarding merocyanine.
No. 48-41204, No. 50-40662, JP-A No. 56-25728, No. 58-10753, No. 5
No. 8-91445, 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, acetone, dimethylformamide, or fluorinated alcohol described in Japanese Patent Publication No. 40659/1984 is used in advance. It is used by dissolving it in a hydrophilic organic solvent.

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 coupler includes an open-chain ketomethylene compound and a so-called two-equivalent type coupler.
〇-aryl substituted coupler, active point -〇-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound substituted coupler and active point succinimide compound substituted coupler, active point fluorine substituted coupler, active point chlorine or bromine substituted coupler 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. Pat. No. 2,875.057, U.S. Pat. No. 3,265.50Ei, U.S. Pat. , same 3
, No. 725,072, No. 3,891,445, West German Patent No. 1,547.8138, West German Application Publication No. 2,219,
No. 917, No. 2,281,381, No. 2,414.0
No. 06, British Patent No. 1.425.02Q, Special Publication No. 1983-
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. 5B
-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. 2,900,788 and 2,983.
, No. 908, No. 3,082,853, No. 3,127,
No. 269, No. 3,311.476, No. 3,419,3
No. 91, No. 3,519,429, No. 3.558,31
No. 9, No. 3.582.322, No. 3,815,501
No. 1, No. 3,834,908, No. 3,891,44
No. 5, West German Patent No. 1,810.41114, West German Patent Application (OLS), No. 2,408,885, No. 2,41
No. 7,945, No. 2,418,959, No. 2,424
．． No. 467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 51-2
No. 0826, No. 52-58922, No. 49-1295
No. 38, No. 49-74027, No. 50-159336
No. 52-42121, No. 49-74028, No. 50-60233, No. 51-26541, No. 53-
55122, Japanese Patent Application No. 55-110943, and the like.

Further, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers include US Pat. No. 2,389,929 and US Pat.
, No. 434,272, No. 2,474.2113, No. 2
, No. 521,1108, No. 2,895.82E1, No. 3,034,892, No. 3,311,478, No. 3
, No. 458.315, No. 3,478,583, No. 3,
No. 583,971, No. 3.591.383, No. 3,7
No. 87,411, No. 3,772,002, No. 3.93
3.494, 4,004,929, West German Patent Application (OLS) 2,414,830, 2,454,
No. 329, JP-A-48-59838, JP-A No. 51-260
No. 34, No. 48-5055, No. 51-146827, No. 52-69624, No. 52-90932, No. 5
Examples thereof include those described in Japanese Patent Publication No. 8-95346 and Japanese Patent Publication No. 11572-1972.

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 the conventional method, and the amount of the above-mentioned coupler added is not limited, but it is 1 x 10 - per mole of silver.
3 to 5 mol is preferable, more preferably I
2-5 x 10".

In addition to the above, the photographic element of the present invention may contain various photographic additives, such as antifoggants, stabilizers, and ultraviolet absorbers described in Research Φ Disclosure No. 17843.

A color stain inhibitor, a fluorescent whitening agent, a color image fading inhibitor, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent, etc. can be used.

In the photographic elements of this invention, the hydrophilic colloids used to prepare the emulsions include gelatin, derivative gelatins, graft polymers of gelatin and other polymers, albumin, proteins such as casein, hydroxyethyl cellulose derivatives, carboxymethyl cellulose, etc. Examples include cellulose derivatives such as cellulose derivatives, starch derivatives, polyvinyl alcohol, polyvinylimidazole, polyacrylamide, and other single or copolymer synthetic hydrophilic polymers.

Supports for photographic elements of the invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, and reflective layers. Or a transparent support used in combination with a reflector, such as a glass plate, a polyester film such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, and other ordinary transparent supports. These supports may be 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
, 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 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, An 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.
The effects of the present invention are most significant when all of these photosensitive emulsion layers are composed of the silver chlorobromide emulsion of the present invention.

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. Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included.

[Effects of the Invention] According to the great invention, even when processed using a color developing solution at a low replenishment amount, constant and appropriate photographic performance can be maintained over a long period of time without being affected by changes in bromide ion concentration, and 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 on both sides with polyethylene, the following layers were sequentially coated from the support side, and photographic element sample No.
1 was created.

Layer 1...1.2g/gold gelatin, silver amount 0.32g
blue-sensitive silver chlorobromide emulsion (silver bromide content 90 mol%) of 0.50 g/rrfQ) of 0.90 g/m2 of yellow coupler (y -t), and a layer containing 15 mg/m'' of exemplary compound (1).

Layer 2---0.70g/m' gelatin, 12mg/m'
(7) Anti-irradiation dye (AI
-1) An intermediate layer consisting of 6 mg/g of (AI-2).

Layer 3... 1.25 g/m'' gelatin, silver content 0.
25 g/m'' green-sensitive silver chlorobromide emulsion (silver bromide content 70
mol %), 0.82 g/l dissolved in 0.30 g/m2 of dioctyl phthalate! 1' of magenta coupler (M-1).

54 - Intermediate layer consisting of 1.20 g/m' of gelatin.

Layer 5... Gelatin of 1.2Qg/m'', silver amount OJ
Red-sensitive silver chlorobromide emulsion (silver bromide content 70 mol %) of Og/m, dissolved in 0.20 g/m' dioctyl phthalate, containing 45 g/m' cyan coupler (C-1) layer to do.

Layer 6, -- 1. QQg/rrI' gelatin and 0
- 0, dissolved in 20 g/ml dioctyl phthalate;
Layer containing 30 g/rn'' ultraviolet absorber (UV-1).

N7... Layer containing 0.50 g/m2 of gelatin.

In addition, as a hardening agent, 2,4-dichloro-6-hydroxy-S-) riazine sodium in N2,4 and 6,
Each was added in an amount of 0.017 g per 1 g of gelatin.

Below is the margin (Y-1) t L t (AI-1) (AI-2) (UV-1) Sample No. 2 was prepared in the same manner as Sample No. 1) except that Exemplified Compound (1) was replaced with Exemplified Compound (3).
Or Sample No. 3 to No. 00 in the same manner as Sample No. 1 except that Comparative Compound (1) or (2) below was used.
8 was created.

Comparative Compound (1) Comparative Compound (2) Each of the above samples Nos. 001 to 8 was exposed through an optical wedge and then processed in the first step.

Processing steps (38°C) Color development 1 minute 30 seconds Bleach-fixing 1 minute 30 seconds washing with water 1 minute drying 90-90°C 2nd generation The composition of the processing solution is as follows.

[Color developer]

Pure water 900mJl Benzyl alcohol 151m Hydroxyamine sulfate 2.08 Potassium bromide
0.6g sodium chloride
l・0g potassium sulfite
2.0g triethanolamine 2.
0g color developing agent (as shown in Table 1) 8.0g
! -Hydroxyethylidene-31.1-diphosphonic acid (
60% aqueous solution) 1.5 liters potassium carbonate 32gWhite
x BB (50% aqueous solution) (Fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) Add 2 mjl of pure water to make one sentence, and adjust the pH to 11.0 with 20% potassium hydroxide or 10% dilute sulfuric acid.

[Bleach-fix solution] Pure water 550 layers Iron ethylenediaminetetraacetate (m) Ammonium salt 135g Ammonium thiosulfate 85g Sodium hydrogen sulfite 10g Sodium metabisulfite
2g ethylenediaminetetraacetic acid-2 sodium A
Add 20g sodium bromide and 10g pure water to make a monochrome mixture, and adjust the pH with aqueous ammonia or dilute sulfuric acid.
= 7.0.

Sensitometry was performed on each sample after the above treatment,
The development completion time was determined and shown in Table 1. The development completion time was expressed as the processing time required to reach the maximum density of 90, assuming that the maximum density of yellow when color development was carried out at 38° C. for 10 minutes was 100.

Below is a color developing crude drug for margin comparison (OD-3): 3/2 H2BO3.H,0 (OD-6) As is clear from the results in Table 1, silver halide is not substantially silver chlorobromide. Compared to the sample in which the color developing agent is substantially silver chlorobromide and the color developing agent is the exemplary compound (2) of the present invention, the bromide ion concentration in the color developing solution is O, 8g/l.

Even when changing from 1 to 5 g/fL to 3.5 g/fL, the color density did not change much, indicating high processing stability. In contrast, the conventionally known color developing agent CD
In the case of -3 or an-e, regardless of the composition of silver halide, there is a drawback that the color density decreases as the bromide ion concentration in the color developing solution increases. I understand. Note that Table 1 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. 32 of Example 1 was exposed and developed in the same manner as in Example 1 using the same processing solution as in Example 1. A 0 color developing solution was prepared by changing the color developing agent as shown in Table 2 and was processed. The zero color development time used was varied as shown in Table 2. The treatment temperature was 38°C.

The obtained sample was stored for 10 days under irradiation with a xenon lamp, and changes in cyan concentration were measured. At this time, the yellow stain density of the unexposed area of the same sample was measured and similarly shown in Table 2.

As is clear from the results in Margin Table 2 below, when the color developer uses CD-3 or Cl1-8 as the color developing agent, there is no big difference in the rate of fading no matter how many seconds the color development time is. It can be seen that the color fading is particularly large in the case of CD-8 compared to CD-3. This also applies to the yellow stain density (Dmin) of the unexposed area.

On the other hand, the color developing agent exemplified compound (1) of the present invention is (2)
), when the color development processing time is 190 seconds or more, the color fading is large and the storage stability is extremely low. This also applies to the yellow stain density (Dmin) of the unexposed area.

However, it can be seen that when the color development time is 150 seconds or less, the storage stability is rapidly improved, resulting in more 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 amount of the color-forming developing agent in the film may also be closely related. Ru.

Procedural amendment letter September 8, 1986

Claims (10)

[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 one layer of A silver halide color photographic light-sensitive material in which the silver halide emulsion in the light-sensitive emulsion layer is substantially a silver chlorobromide emulsion and contains 20 mg/m^2 or more of a compound represented by the following general formula [I], 1. A method for processing a silver halide color photographic light-sensitive material, which comprises developing at a temperature of 30° C. or more and 150 seconds or less using a color developing solution containing an N-hydroxyalkyl-substituted p-phenylenediamine derivative. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 may be the same or different, and each represents an alkyl group that may have a substituent. (2) 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 90 mol% or less. A method for processing a silver halide color photographic light-sensitive material as described in . (3) The silver halide color photographic light-sensitive material according to claim 1 or 2, characterized in that the total coating amount of silver in the silver halide color photographic light-sensitive material is 1 g/m^2 or less. Processing method. (4) 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 3. (5) Claim 4, 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 . (6) A method for processing a silver halide color photographic light-sensitive material according to claim 4, characterized in that processing is performed with a color developing solution containing 1.5 x 10^-^2 moles or more of bromide. (7) The method for processing a silver halide color photographic light-sensitive material according to claim 3, wherein the total amount of coated silver is 0.8 g/m^2 or less. (8) N-hydroxyalkyl-substituted-p-phenylenediamine derivative is 3-methyl-4-amino-N-ethyl-
8. The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 7, characterized in that the N-β-hydroxyethylaniline salt is used. (9) The silver halide according to any one of claims 1 to 8, characterized in that 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. (10) A method for processing a silver halide color photographic material according to claim 9, wherein the color photographic material is processed at a replenishment amount of 200 ml/m^2 or less during continuous processing.