JPH0648377B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a color development processing method of a silver halide color photographic light-sensitive material (hereinafter referred to as a light-sensitive material or a photographic material), and more specifically, a change in replenishment amount and evaporation. A new dye image that is less dependent on fluctuations in bromide ion concentration and processing time caused by the effect of the above, does not impair rapidity, and is excellent in light brownness and has a high storage stability, and has excellent color reproducibility. The present invention relates to a processing method, and particularly to a method which provides a small replenishment amount, high processing stability, and cyan color contamination in an unexposed area and good color reproducibility.

[Prior Art] The processing of a light-sensitive material basically comprises two steps of color development and desilvering, and desilvering comprises a bleaching and fixing step or a bleach-fixing step. In addition to this, rinse treatment, stabilization treatment, and the like are added as additional treatment steps.

In color development exposed silver halide is reduced to silver while the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. During this process, halogen ions generated by the reduction of silver halide are eluted and accumulated in the developer. Separately, components such as inhibitors contained in the silver halide photographic light-sensitive material are also eluted and accumulated in the color developing solution. In the desilvering step, silver produced by development is bleached with an oxidizing agent, and then all silver salts are removed from the photographic light-sensitive material as soluble silver salts with a fixing agent. There is also known a one-bath bleach-fix processing method in which the bleaching step and the fixing step are collectively processed at the same time.

In the color developing solution, the development-inhibiting substance is accumulated by developing the photographic light-sensitive material as described above, while the color-developing agent and benzyl alcohol are consumed or accumulated in the photographic light-sensitive material and taken out. The concentration decreases. Therefore, in the development processing method in which a large amount of silver halide photographic light-sensitive material is continuously processed by an automatic developing machine or the like, the components of the color developing solution are kept within a certain concentration range in order to avoid a change in development finish characteristics due to a change in component concentration. Means are needed. As such means, a method of replenishing a replenisher for diluting unnecessary increasing components and supplementing deficient components is usually adopted. Since the replenishment of this replenisher inevitably causes a large amount of overflow and is discarded,
This method has become a major economic and pollution problem. Therefore, in recent years, in order to reduce the overflow solution, a so-called concentrated low replenishment method in which these replenishers are concentrated and replenished in small amounts is widely used. Alternatively, a method in which a regenerant is added to the overflow solution to use it again as a replenisher is also used. Proposed and put to practical use.

[Problems to be Solved by the Invention] These are methods in which the replenishment amount is substantially reduced. If the replenishment amount is extremely reduced, the organic inhibitor and halogen ion concentration eluted in the developer will undergo a large concentration change even with a slight replenishment amount error.
In addition, it is also susceptible to the effect of concentration due to evaporation, and normally the concentration of the above-mentioned fatigue accumulation increases. For example, when the halogen ion concentration rises, the development reaction is suppressed, or the leg portions of the characteristic curve are further suppressed, which causes a problem of high contrast. To avoid this, halogen ions are removed from the overflow solution by ion exchange resin or electrodialysis, and a regenerant is added to replenish the deficient components generated during development and the deficient components lost during the regeneration process, and regenerated as a replenisher. The method to use is proposed.

Regeneration by these ion exchange resins and electrodialysis and concentrated low replenishment methods are easily affected by fluctuations in bromide ion concentration due to the effects of evaporation and regeneration operations. Separately, there is a difference in processing amount, especially at the beginning of the week when orders are high and orders are received. The difference between the high season and the off-season is the maximum difference of 1: 5, and the composition of the treatment liquid is drastically different because of the influence of evaporation and the difference in the amount of replenisher. There is a drawback that ends up.

Therefore, in the low replenishment treatment and the regeneration method, we are trying to quantitatively analyze the components for each regeneration and make the composition constant, so that it is not possible to carry out these regeneration treatments and low replenishment treatments at a laboratory or a minilab without special skills. Often difficult.

Such problems are mainly caused by changes in the bromide ion, which is a development inhibitor.For example, by reducing the amount of silver bromide in a photographic material, the amount of accumulated bromide ion is reduced, or evaporation or replenishment is performed. It has also been proposed to reduce fluctuations in the concentration of bromide ions due to error in the amount (see Japanese Patent Application Nos. 173,189 / 59, 205,540, etc.).

It is presumed that these problems can be solved by, for example, reducing the average grain size of silver halide in the photographic material or improving the developability by reducing the amount of coated silver. In a color developing solution using a certain 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, improving the developing property causes a change in the bromide ion concentration in the developing solution. The result is the opposite of the expectation that it will be easily received and the processing stability will be impaired.

However, it is an important issue to shorten the processing time and increase the processing stability.

Conventionally, in color paper processing consisting essentially of silver chlorobromide emulsion, color development is 33 ° C, 3 minutes 30 seconds-bleach-fixing 33 ° C, 1
Minutes 30 seconds-Washing 3 minutes (or stabilizing treatment 3 minutes) -Drying. The total processing time is generally about 8 minutes, but the strong demand of the times is the above-mentioned low replenishment in the economic sense, but short-time processing is also strongly demanded from the viewpoint of shortening the delivery time. ing.

However, as described above, speeding up and stabilization of processing or low replenishment are contradictory problems, and can be said to be a trade-off relationship.

That is, if the replenishment rate is lowered, the concentration of bromide ion as an inhibitor and the concentration of a sulfur compound or a mercapto compound as an emulsion stabilizer are increased, impairing the rapidity and impairing the processing stability.

However, various measures have conventionally been taken to speed up color development for speeding up. In particular, the above-mentioned developing agents that have been used as the most suitable developing agents for silver chlorobromide emulsions for a long time have low hydrophilicity, so that the penetration of the color developing agent into the light-sensitive material is slow and Various penetrants have been studied, and for example, a method of adding benzyl alcohol to a color developing solution to accelerate color developing is widely used. However, in this method, if the treatment is not performed at 33 ° C for 3 minutes or more,
The color was not sufficiently developed, and in addition to that, there was a drawback that it was easily affected by the delicate bromide ion concentration. A method of increasing the pH of the color developing solution is also known, but when the pH is 10.5 or more, the oxidation of the color developing agent becomes remarkably fast, and there is no suitable buffer solution, so it is susceptible to pH changes and stable. However, there is a problem in that the photographic characteristics described above cannot be obtained and the dependence of processing time increases.

A method of increasing the activity by increasing the color developing agent in the color developing solution is also known, but it is said that the color developing agent becomes an expensive processing solution because it is very expensive, and at the same time, the main agent is difficult to dissolve in water and easily precipitates. Instability also occurs and it is not practically usable.

On the other hand, there is known a method of preliminarily incorporating a color developing agent in a light-sensitive material in order to achieve rapid color development. For example, a method of incorporating a color developing agent in the form of a metal salt is known (US Pat. No. 3,719,492), but with this method, the raw storability of the light-sensitive material is poor and fogging occurs before use, and fogging during color development. It had the drawback of being easy.

Furthermore, in order to inactivate the amine part of the color developing agent,
For example, a method of forming a Schiff salt and incorporating a color developing agent (US Pat. No. 3,342,559, Research Disclosure, 1976).
No. 15159) is also known, but these methods have a drawback that color development cannot be started until the color developing agent is hydrolyzed with alkali, and the color development is rather delayed.

Furthermore, when the color developing agent is directly incorporated, in addition to the drawback that the emulsion during storage is fogged because of the unstable color developing agent, the emulsion film quality becomes weak and various processing problems occur. there were.

Furthermore, it is known that 3-pyrazolidones are added to a black-and-white developer containing a developer such as hydroquinone to accelerate development (eg, LFA Mason, Photographi
c Processing Chemistry 103-107 pages, published by Focal Press, 1
966). The fact that this compound is incorporated in the photosensitive material is
Although described in British Patent No. 767,704, in the technology described in the above-mentioned patent specification, the black-and-white light-sensitive material or the reversal color light-sensitive material is incorporated, the purpose is to promote only black-and-white development, Also, JP-A-53-52422
In order to prevent a decrease in sensitivity of a color light-sensitive material containing a 2-equivalent magenta coupler having an oxy-type organic split-off group at an active site in an unexposed state, 3-pyrazolidones are contained in the light-sensitive material. However, these technologies are
It is not suitable as a rapid method for stabilizing the color development process with a low replenishment process.

Further, as a method of accelerating color development by a conventionally known accelerator, US Pat. Nos. 2,950,970 and 2,515,147 are known.
No. 2,496,903, 4,038,075, 4,119,462,
British Patents 1,430,998 and 1,455,413, JP-A-53-1
No. 5831, No. 55-6245, No. 55-6245.
1, No. 55-62452, No. 55-62453,
The compounds and the like described in JP-B-51-12322 and JP-B-55-49728 were examined, but most of the compounds have insufficient accelerating effect, and compounds showing a high accelerating effect produce fog. However, it is not suitable as a method for improving processing stability.

Further, providing a substantially light-insensitive silver halide emulsion layer in a light-sensitive material to accelerate development is disclosed in JP-A-50-2320.
No. 25, No. 56-14236, British Patent No. 1,378,577,
Known as OLS No. 2,622,922, its function is to adsorb unnecessary halogens released during development and development inhibiting substances such as unnecessary leaving groups of DIR couplers and DIR couplers. Although it does not accelerate the development, its development promoting effect is small, and although it is effective for the fluctuation of the iodide ion concentration, no processing stabilizing effect is obtained for the fluctuation of the bromide ion concentration.

On the other hand, the speed of color development differs depending on the type of para-phenylenediamine derivative used and is said to depend on the redox potential. Among these color developing agents, N,
N-diethyl-p-phenylenediamine sulfate or 3-methyl-4-
N-alkyl-substituted low water-soluble color developing agents such as amino-N, N-diethylaniline hydrochloride have high developing activity and can be accelerated, but the dark brown color of the coloring dye after processing is not preferable. It is known. On the other hand, it is said that it has a high developing activity and is preferable (US Pat. No. 3,656,950, concentric
(See No. 3,658,525) 3-Methyl-4-amino-N-ethyl-N-β
-Methoxyethylaniline-di-p-toluenesulfonate is certainly quick, but bromide ion concentration stability is not obtained and yellow stain is remarkably generated in the unexposed area of the photographic light-sensitive material after processing. In particular, when processed for a short time, there is a drawback that the color developing agent remains and causes the generation of rough stains, so that it cannot be used in rapid processing.

On the other hand, 3-methyl-4 in which a water-soluble alkylsulfonamide group or hydroxyalkyl group was introduced into the N-alkyl group
-Amino-N-ethyl-β-methanesulfonamide ethylaniline sesquisulfate monohydrate and 3-methyl-4
-Amino-N-β-hydroxyethylaniline sulphate has a redox potential as seen in Photographic Science and Engineering Vol.8, No. 3.5-June, 1964, P.125-137. It was said that there was not much difference in the half-wave potentials shown and that both had weak developing activities.

Therefore, there is almost no color developing agent that can substantially develop the silver chlorobromide emulsion and has excellent storage stability of the dye image, and generally 3-methyl-4-amino-N-ethyl-N-β-methane. Sulfonamidoethylaniline sulphate has achieved this goal by using it with benzyl alcohol.

However, in this case, as described above, it is easily affected by the change in the bromide ion concentration. Further, in the concentrated and low replenishment process in which the replenisher is reduced, another problem is an increase in mixing and accumulation of other treatment liquid components. This is because the tank liquid is renewed with the replenishing liquid at a low rate due to the decrease in the replenishing amount, and the service life of the liquid is prolonged.
Contamination of other processing solutions is caused by so-called back contamination in which the processing solution components immediately after development are brought into the color developing solution by splashing of the adjacent processing solution in the processor, a transport leader, a belt or a hanger for hanging the film. Be done. Among these accumulated mixed components, the thiosulfate ion as the fixing agent accelerates the development. That is, this problem particularly strongly occurs when the bleach-fixing process is performed directly after color development. Particularly by promoting the shoulder of the photographic characteristic curve, a significant increase in contrast occurs. Further, an increase in the content of a metal salt as a bleaching agent, especially a ferric salt, promotes the decomposition of hydroxylamine as a preservative to generate ammonia ions. This decomposition reaction is greatly accelerated above 30 ° C. The generation of this ammonia ion promotes physical development similarly to thiosulfate ion, and has a drawback that high contrast is obtained.

Therefore, even if the amount of replenishment is reduced to improve economic and environmental pollution, rapid processing is possible, the photographic performance is maintained constant, and the active ingredient is decomposed even when the processing solution is used for a long time. At present, there is a strong demand for the emergence of a color developing solution that can be stably processed without changing the photographic processing performance.

Therefore, a first object of the present invention is to maintain constant and appropriate photographic performance for a long period of time without being affected by changes in bromide ion concentration even when processed with a low replenishing amount using a color developer. It is an object of the present invention to provide a rapid and stable method for processing a silver halide color photographic light-sensitive material in which the color-developing dye or the uncolored portion thus obtained does not turn brown or discolor even after long-term storage.

As a result of various studies to achieve the above-mentioned first object of the present invention, the present inventor succeeded in finding a unique color developing agent which is hardly affected by the bromide ion concentration during the development of a specific silver halide. And, the storage stability of the obtained color forming dye was also greatly improved, but when a normal continuous process for supplementing the inactivation of the development by the process by supplementing the replenishing solution for a long time, The problem that cyan color contamination is likely to occur in the unexposed area was investigated, and a method for solving this problem was further investigated.

[Means for Solving Problems] The inventors of the present invention have proposed a color photographic light-sensitive material using a specific silver halide, that is, an emulsion mainly containing silver chlorobromide (in particular, a silver bromide content of 90 mol% or less). We have found the surprising fact that when the color developing agent is an N-hydroxyalkyl-substituted-p-phenylenediamine derivative, the resulting dye concentration hardly changes even when the bromide ion concentration changes. The characteristic feature of this color developing agent is that it cannot be obtained with a color photographic light-sensitive material substantially containing a silver iodobromide emulsion containing 0.5 mol% or more of silver iodide. This is unexpected because it has been used exclusively for the development of silver bromide emulsions, and in particular, even when the bromide ion concentration is greatly increased during the development of color photographic light-sensitive materials using substantially silver chlorobromide emulsions. The fact that the development speed does not delay is unexpected and cannot be understood from the oxidation-reduction potential and half-wave potential of common color developing agents, and perhaps the optimal balance between development speed and coupling speed is maintained. It wouldn't have happened unless it was hit, and it was amazing.

However, the present inventor has encountered the following obstacles. that is
N-Hydroxyalkyl-substituted-p-phenylenediamine A color developer that is used rapidly when used and does not undergo changes in bromide ion concentration, and can be developed especially under a high bromide ion concentration. The storage stability of the obtained color-forming dye, although the great advantage that the processing stability can be significantly reduced
In particular, it has been found that there is a drawback that light brownness is lowered. The storage stability of the dye image is fatal, especially in the case of a printing material, which is a serious obstacle.

The present inventor further diligently worked to solve this problem,
We found that it is not because the storage stability of the dye itself is low, but because the color developing agent easily remains in the color photographic light-sensitive material, and in particular, it can be solved by performing the color developing time in a short time. . However, shortening the color development time cannot be achieved unless the developing processability of the color photographic light-sensitive material is sufficiently improved, and cannot be unconditionally shortened.However, low replenishment and process stability do not impair the storage stability of the dye image. In order to achieve the property, it was found that it is a condition that processing is performed at 30 ° C. or higher and within 150 seconds using the color developing solution of the present invention.

In this case, there is a problem that a conventional photographic light-sensitive material as it is cannot develop a sufficient photographic image due to insufficient development time. Therefore, the present inventor has further studied, and at least one layer, and preferably all the light-sensitive emulsion layers, of the color developing agent of the present invention is used for the low replenishment processing without being affected by the increase of the bromide ion concentration. The silver halide emulsion is substantially a silver chlorobromide emulsion, and the film swelling speed T1 / 2 of the binder is
The development speed is improved by treating a color photographic light-sensitive material which is 30 seconds or less with a developing solution containing an N-hydroxyalkyl-substituted-p-phenylenediamine derivative. It was possible to achieve the first object without deteriorating the stability of the dye image for the first time by rapidly performing color development.

However, when the present inventor processed using this processing method, a completely unexpected problem occurred. That is, when the photosensitive material was subjected to continuous processing for a long period of time under the condition of 30 ° C. or more and 150 seconds or less with a developing solution containing an N-hydroxyalkyl-substituted-p-phenylenediamine derivative, cyan color contamination on unexposed areas Was found to be likely to occur.

As a result of extensive studies for solving this problem, the use of the cyan coupler represented by the above-mentioned general formula [I] in the red-sensitive emulsion layer can solve the above problem quite surprisingly. It became clear that it was possible.

As a result, in the method of developing a silver halide color photographic light-sensitive material, the silver halide emulsion of at least one light-sensitive emulsion layer is substantially a silver chlorobromide emulsion, and the film swelling speed T1 / 2 of the binder is T1 / 2. Is 30 seconds or less, and the cyan coupler represented by the following general formula [I] (hereinafter,
The silver halide color photographic light-sensitive material containing the cyan coupler of the present invention) is substituted with N-hydroxyalkyl-substituted-p
It has been found that the above object can be achieved by performing development processing using a color developer containing a phenylenediamine derivative at 30 ° C. or higher and 150 seconds or shorter.

General formula [I] In the formula, one of R and R ₁ is a hydrogen atom, and the other is at least a linear or branched alkyl group of 2 to 12, and X is a hydrogen atom or the N-hydroxyalkyl-substituted-p-phenylenediamine derivative It represents a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent, and R ₂ represents a ballast group.

In the present specification, “substantially silver chlorobromide emulsion” means that a small amount of silver iodide may be contained in addition to silver chlorobromide.
For example, it means that 0.3 mol% or less, and more preferably 0.1 mol% or less of silver iodide may be contained. However, silver chlorobromide emulsions containing no silver iodide are most preferred in the present invention.

Hereinafter, the present invention will be described in more detail.

The hydrophilic binder used for coating the silver halide of the color photographic light-sensitive material is usually gelatin, but sometimes a high-molecular polymer is used, and the film swelling speed T1
/ 2 must be less than 30 seconds, the film swelling rate T1 / 2 of the binder can be measured according to any method known in the art, for example A. Green Photo.Sci.En.
It can be measured by using a swellometer (swelling meter) of the type described in g., Vol.19, No.2, P.124-129, and T 1/2 is 30 ° C for 3 minutes in color development. 90% of the maximum swollen film thickness reached after 30 seconds of treatment is the saturated film thickness,
It is defined as the time to reach 2 (see Fig. 1).

The binder of the photographic constituent layer used in the silver halide color photographic light-sensitive material of the present invention has a swelling speed T1 / 2 of 30 seconds or less, and the smaller the better, the smaller the lower limit is. Two seconds or more is preferable because failure is likely to occur. Particularly preferably, it is 20 seconds or less, and most preferably 15 seconds or less. When it is longer than 30 seconds, the storage stability of the dye image is low and sufficient dye formation cannot be obtained within 150 seconds. The film swelling speed T1 / 2 can be adjusted by the amount of the hardener used.

The photosensitive emulsion layer of the silver halide color photographic light-sensitive material processed according to the present invention may have at least one layer consisting essentially of a silver chlorobromide emulsion, but all of the photosensitive emulsion layers are chlorobrominated. It is preferably composed of a silver emulsion. As the silver chlorobromide has a smaller mol% of silver bromide, sufficient dye formation can be obtained even in a short time of color development. Therefore, the silver bromide content is preferably 90 mol% or less, and 70 mol% or less 40 mol% The above is the most preferable result.

Further, the smaller the amount of coated silver, the more preferable it is in that there is no delay in development with respect to the increase in bromide and sufficient dye formation can be performed for a short time, and the maximum effect is obtained when it is 1 g / m ² or less, particularly 0.8 g / m ² or less. can get. The color development treatment is 30 ° C. or higher and 150 seconds or less, preferably 33 ° C. or higher and 120 seconds or less, and most preferably 3
It is required to process at 5 ℃ or more and 90 seconds or less, 30 ℃ or more, 1
When the treatment is carried out for 50 seconds or longer, the storage stability of the dye deteriorates. In particular, the processing time is more important than the temperature, and if it exceeds 150 seconds, the light brownness of the cyan dye remarkably increases, which is not preferable. The processing temperature is higher than the storage stability of the dye in order to finish the development in a short time, and is preferably 30 ° C. or higher and 50 ° C. or lower as the higher the processing time is, the more preferable, and particularly preferably 33 The temperature is not lower than 0 ° C and not higher than 48 ° C, most preferably not lower than 35 ° C and not higher than 43 ° C.

The developing agents effective in the present invention are quaternary ammonium salts of N-hydroxyalkyl-substituted-p-phenylenediamine compounds, especially those represented by the following general formula.

In the formula, R ₁ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and R ₂ is a hydrogen atom or 1 to 4 carbon atoms. Is an alkyl group having R 1 and R ₃ may have a hydroxyl group 1
Is an alkyl group having 4 to 4 carbon atoms, A is an alkyl group having at least one hydroxyl group and optionally having a branch, and more preferably Is. R ₄ , R ₅ and R ₆ each represent a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms which may have a hydroxyl group, and at least one of R ₄ , R ₅ and R ₆ is a hydroxyl group. Alternatively, it is an alkyl group having a hydroxyl group. n ₁ , n ₂ and n ₃ are 0, ₁ , 2 or 3 respectively, and HX is hydrochloric acid, sulfuric acid, p-
Represents toluene sulfonic acid, nitric acid or phosphoric acid.

Such p-phenylenediamine color developing agents are unstable with their free amines and are commonly used as salts (most commonly identified by the above formula). Typical example is 4-amino-3-methyl-N-ethyl
-N- (β-hydroxyethyl) -aniline salt and 4-amino-N-
Ethyl-N- (β-hydroxyethyl) -aniline salt may be mentioned.

Preferably, in the present invention, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate-hydrate [which is commercially available under the name CD-4, In the color photo system of the part (for example, Eastman Kodak Company
C41 system, and Konishi Rokusha Kogyo Co., Ltd. CNK-4 system, which are used for developing a color negative film), have been found to be particularly effective.

Preferred N-hydroxyalkyl-substituted-p for use in the present invention
-Phenylenediamine derivatives include the followings, but are not limited to these exemplified compounds.

[Exemplified compound]

(1) (2) (3) (Four) (Five) (6) (7) (8) Hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid salt of the compounds (1) to (8) are particularly preferable.

Among these exemplified compounds No. (1), (2), (6), (7) and
(8) is preferably used, and particularly Nos. (1), (2) and (6) are preferably used. Furthermore, especially 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, and more preferably in the range of 3 g to 30 g per processing solution.

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

The color developing solution of the present invention preferably has a bromide ion concentration of 5 × 10 ⁻³ mol or more, but in the present invention, the higher the bromide ion concentration is, the more the replenishment amount is lowered, which is preferable. In the conventional developing method, it was said that bromide was more preferable as it suppressed the development reaction and was lower, but in the combination of the color photographic light-sensitive material and the developing solution of the present invention, the higher the bromide is, the more preferable it is, and the object of the present invention was achieved. To be done. In other words, in the present invention, the replenishment amount can be reduced because it is less affected by bromide.

The bromide ion concentration is preferably 1 × 10 ^-2 mol or more, particularly preferably 1.5 × 10 ^-2 mol or more. If the bromide ion concentration is too high, development is suppressed and the influence of the bromide ion concentration begins to occur. ^-2 mol or more is not preferable. The chloride concentration has no effect.

The color photographic light-sensitive material of the present invention is a multi-layer color photographic light-sensitive material having three or more layers each containing a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer. / 2 that is the maximum effect when the film swelling speed T1 / 2 is 30 seconds or less, the total film thickness is 14
μm or less, preferably 13 μm or less, particularly preferably 12 μm
m or less, but in any case, T1 / 2 is preferably 30 seconds or less.

Next, the cyan coupler used in the red-sensitive silver halide emulsion layer according to the present invention will be described.

The cyan coupler of the present invention can be represented by the above general formula [I], and the general formula [I] will be further described.

In the present invention, the linear or branched alkyl group having 2 to 12 carbon atoms represented by R ₁ and R in the general formula [I] is, for example, an ethyl group, a propyl group or a butyl group.

In the general formula [I], the ballast group represented by R ₂ has a size that gives the coupler molecule sufficient bulkiness so that the coupler cannot substantially diffuse from the layer to which the coupler is applied to other layers. And an organic group having a shape. A typical ballast group has a total carbon number of 8 to 32.
Examples of the alkyl group or aryl group are, but the total number of carbon atoms is preferably 13 to 28. These alkyl group and aryl group may have a substituent, and examples of the substituent of this aryl group include an alkyl group, an aryl group,
Alkoxy group, allyloxy group, carboxy group, acyl group, ester group, hydroxy group, cyano group, nitro group,
Carbamoyl group, carbonamido group, alkylthio group,
Examples thereof include an arylthio group, a sulfonyl group, a sulfonamide group, a sulfamoyl group, and halogen, and examples of the substituent of the alkyl group include the same substituents as those mentioned for the aryl group except the alkyl group.

The preferred ballast group is represented by the following general formula.

R ₃ represents an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and this aryl group may have a substituent. Examples of the substituent include an alkyl group, a hydroxy group, a halogen atom, an alkylsulfonamide group and the like, and the most preferable one is a branched alkyl group such as a t-butyl group.

The coupling-off group defined by X in the general formula [I] determines the number of equivalents of the coupler and controls the coupling reactivity, as is well known to those skilled in the art. Typical examples are chlorine, halogen represented by fluorine, aryloxy group, substituted or unsubstituted alkoxy group, acyloxy group, sulfonamide group, arylthio group, heteroylthio group, heteroyloxy group, sulfonyloxy group, carbamoyl. An oxy group etc. are mentioned. As a more specific example, JP-A-50-1013
No. 5, No. 50-120334, No. 50-130441
No. 54, No. 54-48237, No. 51-146828,
54-14736, 47-37425, 50
No. 123341, No. 58-95346, Japanese Patent Publication No. 48
-36894, U.S. Pat. Nos. 3,476,563 and 3,737,316
And No. 3,227,551.

Next, exemplary compounds of the present invention will be described. Examples of the exemplified compound include R ₁ , X,
Examples thereof include those in which R ₂ and R are specified, but are not limited thereto.

The method for synthesizing the exemplified compound of the present invention is shown below, but other exemplified compounds can also be synthesized by the same method.

Synthesis Example of Exemplified Compound (1) [(1) -a] Synthesis of 2-nitro-4,6-dichloro-5-ethylphenol 33 g of 2-nitro-5-ethylphenol, 0.6 g of iodine
And 1.5 g of ferric chloride are dissolved in 150 m of glacial acetic acid.
To this, 75 m of sulfuryl chloride is added dropwise at 40 ° C. over 3 hours. The precipitate formed during the dropping is reacted and dissolved by heating under reflux after the completion of the addition of sulfuryl chloride. Heating under reflux takes about 2 hours. The reaction solution is poured into water and the produced crystals are purified by recrystallization with methanol.
(1) -a was confirmed by nuclear magnetic resonance spectrum and elemental analysis.

Synthesis of [(1) -b] 2-amino-4,6-dichloro-5-ethylphenol 21.2 g of the compound of [(1) -a] was dissolved in 300 m of alcohol, to which a catalytic amount of Raney-Nitzkel was added. Hydrogen was passed through at normal pressure until there was no hydrogen absorption. After the reaction, Raney-Nickel was removed, and the alcohol was distilled off under reduced pressure.
The residue [(1) -b] was subjected to the next acylation without purification.

[(1) -c] 2 [(2,4-di-tert-acylphenoxy)
Acetamido] -4,6-dichloro-5-ethylphenol synthesis 18.5 g of crude amino compound obtained in [(1) -b]
m glacial acetic acid and 16.7 g of sodium acetate were dissolved in the mixture, and an acetic acid solution prepared by dissolving 28.0 g of 2,4-di-tert-aminophenoxyacetic acid chloride in 50 m of acetic acid was added dropwise at room temperature. After dropping for 30 minutes and further stirring for 30 minutes, the reaction solution is poured into ice water. The purified precipitate was filtered and dried,
Recrystallization from acetonitrile twice gives the desired product. The target substance was confirmed by elemental analysis and nuclear magnetic resonance spectrum.

The addition amount of the cyan coupler of the present invention is not limited,
2 × 10 ^{−3 to} 5 per mol of silver in the red-sensitive silver halide emulsion layer
X10 ^-1 mol is preferred, more preferably ^{1x10 -2 to} 5x
It is 10 ^-1 mol.

The processing system of the photographic light-sensitive material of the present invention can use a color developing bath containing the color developing agent according to the present invention. In addition, various other methods including bath treatment,
For example, various processing methods such as a spray method in which the processing liquid is atomized, a web method by contact with a carrier impregnated with the processing liquid, or a developing method with a viscous processing liquid can be used.

In addition to the above, the processing method of the photographic light-sensitive material of the present invention is not particularly limited, and any processing method can be applied. For example, as a typical example, a method of performing bleach-fixing treatment after color development and further washing with water and / or stabilizing treatment if necessary, and performing bleaching and fixing separately after color development,
If necessary, further washing with water and / or stabilizing treatment; or a method of performing pre-hardening, neutralization, color development, stop fixing, water washing, bleaching, fixing, water washing, post-hardening, water washing in this order,
Color development, washing with water, supplemental color development, stop, bleaching, fixing, washing with water, and stability. The developed silver produced by color development is subjected to halogenation bleaching and then color developed again to increase the amount of dye formed. Processing may be performed using any method such as a developing method.

In the color developer used in the present invention, various components that are usually added, for example, sodium hydroxide, an alkali agent such as sodium carbonate, an alkali metal sulfite,
Alkali metal bisulfite, alkali metal thiocyanate, alkali metal halide, benzyl alcohol,
A water softening agent, a thickening agent, a development accelerator and the like may be optionally contained.

Examples of additives other than the above added to the color developing solution include potassium bromide, bromide such as sodium bromide,
Alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole,
In addition to compounds for rapid processing liquids such as 1-phenyl-5-mercaptotetrazole, there are stain inhibitors, anti-sludge agents, preservatives, layering effect accelerators, chelating agents and the like.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution in the bleaching step, those in which metal ions such as iron, cobalt and copper are coordinated with an organic acid such as aminopolycarboxylic acid or oxalic acid, citric acid are generally known. There is. And the following can be mentioned as a typical example of said amino polycarboxylic acid.

Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Iminodiacetic acid Glycol etherdiaminetetraacetic acid Ethylenediaminetetrapropionic acid Ethylenediaminetetraacetic acid disodium salt Diethylenetriaminepentaacetic acid pentasodium salt Nitrilotriacetic acid sodium salt You may contain an agent. When a bleach-fixing solution is used in the bleaching step, a solution having a composition containing a silver halide fixing agent in addition to the bleaching agent is applied. Further, the bleach-fixing solution may further contain a halogen compound such as potassium bromide. And, as in the case of the bleaching solution, various other additives such as pH buffer, fluorescent whitening agent, defoaming agent, surfactant, preservative, chelating agent, stabilizer, organic solvent, etc. Addition,
It may be contained.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc. Compounds forming a silver salt of

Processing other than color development of the silver halide color photographic light-sensitive material of the present invention, for example, bleach-fixing (or bleaching / fixing), and if necessary, rapid processing at various processing steps such as washing and stabilization From the point of view of the above, it is preferable to be carried out at 30 ° C. or higher.

The silver halide color photographic light-sensitive material of the present invention is described in JP-A-58 / 58.
No. 14834, No. 58-105145, No. 58-1
34634 and 58-18631 and Japanese Patent Application No. 5
You may perform water washing alternative stabilization treatment as shown by 8-2709 and 59-89288 etc.

The photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention may contain a dye (AI dye) which is water-soluble or decolorizes with a color developing solution. Examples of the AI dye include oxonol dyes and hemioxonol dyes. Dyes, merocyanine dyes and azo dyes are included. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include British Patent 58
4,609, 1,277,429, JP-A-48-85130,
49-99620, 49-114420, 4
9-129537, 52-108115, 59
No. 25845, No. 59-111640, No. 59-1
11641, U.S. Patents 2,274,782, 2,533,472,
2,956,879, 3,125,448, 3,148,187, 3,1
77,078, 3,247,127, 3,260,601, 3,540,88
No. 7, No. 3,575,704, No. 3,653,905, No. 3,718,472,
Examples thereof include those described in Nos. 4,071,312 and 4,070,352.

These AI dyes generally contain 2 per mole of silver in the emulsion layer.
It is preferable to use x10 ^{-3 to} 5 x 10 ^-1 mol, and more preferably 1 x 10 ^-2 to 1 x 10 ^-1 mol.

The crystal of the silver halide grain may be normal crystal, twin crystal or other crystal, and any ratio of [1.0.0] plane to [1.1.1] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core shell type) in which the inside and the outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (Japanese Patent Application Laid-Open No. 58-113934, Japanese Patent Application No. 59-170).
No. 070) can also be used.

The 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, a method in which seed particles are formed by an acidic method, further grown by an ammonia method having a high growth rate, and grown to a predetermined size may be used. When growing the silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled so that the amount of silver ions corresponding to the growth rate of the silver halide grains as described in, for example, JP-A-54-48521. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

The silver halide grains according to the present invention are preferably prepared as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and thiourea dioxide. Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, or ruthenium, palladium, platinum, rhodium, iridium Water-soluble salt sensitizers such as ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these are used as sensitizers or antifoggants depending on the amount). Etc.) or in combination as appropriate (for example, a gold sensitizer and a sulfur sensitizer are used in combination, Combination etc. with a sensitizer and a selenium sensitizer) to be chemically sensitized.

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after the chemical ripening, at least one kind of nitrogen-containing heteroaryl having a hydroxytetrazaindene and a mercapto group. You may make it contain at least 1 sort (s) of a ring compound.

The silver halide used in the present invention contains a suitable sensitizing dye in an amount of 5 × 10 ^{−8 to} 3 × 10 ^{−3 with} respect to 1 mol of silver halide in order to impart photosensitivity to a desired wavelength region. It may be optically sensitized by adding a mole. Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used. Examples of the sensitizing dye that can be advantageously used in the present invention include the following.

That is, as a sensitizing dye used in a blue-sensitive silver halide emulsion, for example, West German Patent 929,080 and U.S. Pat.
No. 2,493,748, 2,503,776, 2,519,001,
2,912,329, 3,656,959, 3,672,897, 3,6
94,217, 4,025,349, 4,046,572, British patent 1,
No. 242,588, Japanese Patent Publication No. 44-14030, No. 52-24
Nos. 844 and the like can be mentioned. Further, as the sensitizing dye used in the green-sensitive silver halide emulsion, for example, U.S. Patent Nos. 1,939,201, 2,072,908 and 2,2,908,
Representative examples thereof include cyanine dyes, merocyanine dyes and complex cyanine dyes such as those described in 739,149, 2,945,763 and British Patent 505,979. Further, as the sensitizing dye used in the red-sensitive silver halide emulsion, for example, U.S. Patent 2,269,234,
2,270,378, 2,442,710, 2,454,629, 2,7
Typical examples thereof include cyanine dyes, merocyanine dyes and complex cyanine dyes as described in No. 76,280. Furthermore, U.S. Patent 2,213,99
No. 5, No. 2,493,748, No. 2,519,001, West German Patent 929,080
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in JP-A No. 1994-187 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 light-sensitive material of the present invention may be optionally optically sensitized to a desired wavelength range by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination.

A typical example of a particularly preferable spectral sensitization method is, for example, JP-B-43-49, which relates to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 36, No. 43-22884, No. 45-18433
No. 47, No. 47-374443, No. 48-28293,
No. 49-6209, No. 53-12375, and Japanese Patent Laid-Open No. Sho 5
2-23931, 52-51932, 54-8
0118, 58-153926, 59-116.
No. 646, No. 59-116647 and the like.

The combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine is described in, 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, and JP-A 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.

Furthermore, examples of combinations of benzoxazolocarbocyanine (oxacarbocyanine) with other carbocyanines include JP-B-44-32753 and JP-A-46-32753.
11627, JP-A-57-1483, and those relating to merocyanine include, for example, JP-B-48-38408.
No. 48-41204, No. 50-40662, No. 56-25728, No. 58-10753, No. 5
8-91445, 59-166645, 50-
No. 33828 and the like can be mentioned.

Further, as a combination of thiacarbocyanine and other carbocyanine, for example, Japanese Patent Publication No. 43-4932
No. 43-4933, No. 45-26470, No. 4
6-18107, 47-8741, JP-A-59-
114533 and the like, and the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye can be advantageously used.

To add these sensitizing dyes to the silver halide emulsion according to the present invention, dye solutions such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or fluorinated alcohols described in JP-B-50-40659 are prepared in advance. It is used by dissolving it in the hydrophilic organic solvent.

The silver halide emulsion may be added at any time from the start of chemical ripening, during ripening, and at the end of ripening, and in some cases, it may be added immediately before the emulsion coating.

The red-sensitive silver halide emulsion layer according to the present invention contains the cyan coupler of the present invention represented by the above general formula [I]. The red-sensitive silver halide emulsion layer contains a cyan coupler other than the present invention. May be used in combination. However, it is preferable that the amount of the cyan coupler outside the present invention is less than 45 mol% with respect to the total amount of the cyan couplers. The green-sensitive silver halide emulsion layer and the blue-sensitive silver halide emulsion layer according to the present invention may each contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

Examples of the yellow coupler which can be used in the present invention include an open-chain ketomethylene compound, an active point-o-aryl substituted coupler, an active point-o-acyl substituted coupler, an active point hydantoin compound-substituted coupler, which is a so-called 2-equivalent coupler. Active point urazole compound-substituted couplers, active point succinimide compound-substituted couplers, active point fluorine-substituted couplers, active point chlorine- or bromine-substituted couplers, active point-o-sulfonyl-substituted couplers, etc. can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Patents 2,875,057, 3,265,506, 3,408,194, and
3,551,155, 3,582,322, 3,725,072, 3,89
1,445, West German patent 1,547,868, West German application published 2,219,91
7, 2,261,361, 2,414,006, British Patent 1,425,0
No. 20, JP-B-51-10783, JP-A-47-261
No. 33, No. 48-73147, No. 51-102636
No. 50, No. 50-6341, No. 50-123342, No. 50-130442, No. 51-21827, No. 50.
-87650, 52-82424, 52-11
5219, 58-95346, etc. can be mentioned.

Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based and indazolone-based 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. Patents 2,600,788, 2,983,608 and 3,06.
2,653, 3,127,269, 3,311,476, 3,419,391
No. 3,519,429, 3,558,319, 3,582,322,
3,615,506, 3,834,908, 3,891,445, West German patent 1,810,464, West German patent application (OLS) 2,408,665
No. 2, 2,417,945, 2,418,959, 2,424,467,
JP-B-40-6031, JP-A-51-20826,
52-58922, 49-129538, 4
9-74027, 50-159336, 52-
42121, 49-74028, 50-602.
No. 33, No. 51-26541, No. 53-55122
And Japanese Patent Application No. 55-110943.

Further, examples of cyan couplers that can be used in the present invention include various phenol-based and naphthol-based couplers. And 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 that can be used in combination include U.S. Patents 2,369,929 and 2,434,272.
No. 2, 2,474,293, 2,521,908, 2,895,826,
3,034,892, 3,311,476, 3,458,315, 3,4
76,563, 3,583,971, 3,591,383, 3,767,41
No. 1, 3,772,002, 3,933,494, 4,004,929,
West German patent application (OLS) 2,414,830, 2,454,329,
JP-A-48-59838, 51-26034, 48-5055, 51-146827, 52-
69624, 52-90932, 58-953.
No. 46, Japanese Patent Publication No. 49-11572 and the like can be mentioned.

A coupler such as a non-diffusible DIR compound, a colored magenta or cyan coupler, a polymer coupler or a diffusible DIR compound may be used in combination in the silver halide emulsion layer and other photographic constituent layers of the present invention. Non-diffusible DIR compounds, colored magenta or cyan couplers are described in Japanese Patent Application No. 59-193611 by the applicant, and polymer couplers are described in Japanese Patent Application No. 59-1.
Reference can be made to the description of No. 72151, respectively.

The amount of the above-mentioned coupler usable in the present invention is not limited, but is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 × 10 ^{−2 to} 5 × 10 ⁻¹ , per mol of silver.

In order to incorporate the cyan coupler of the present invention in the silver halide emulsion of the present invention, when the cyan coupler of the present invention is alkali-soluble, it may be added as an alkaline solution and it is oil-soluble. In this case, for example, U.S. Pat.Nos. 2,322,027, 2,801,170, and 2,801,17
No. 1, No. 2,272,191 and No. 2,304,940 according to the method described in each of the specifications of the cyan coupler of the present invention in a high-boiling solvent, if necessary in combination with a low-boiling solvent is dissolved, dispersed in fine particles. Is preferably added to the silver halide emulsion. At this time, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents and the like may be used in combination if necessary. Further, two or more kinds of cyan couplers of the present invention may be mixed and used. Further, in the present invention, the method for adding the cyan coupler of the present invention will be described in detail. One or more cyan couplers of the present invention may be added, if necessary, to other couplers, hydroquinone derivatives,
Organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, tri-cresyl phosphate, triphenyl along with anti-fading agents and UV absorbers. Phosphate, di-isooctyl azelate, di-n-butyl sebacate, tri-n-hexyl phosphate, N, N-di-ethyl-caprylamidobutyl, N, N-diethyllaurylamide, n-pentadecylphenyl ether, di- -Octyl phthalate, n-nonylphenol, 3-pentadecyl phenyl ethyl ether, 2,5-di-sec-amyl phenyl butyl ether, monophenyl-di-o-chlorophenyl phosphate or high boiling solvent such as fluoroparaffin, and / or acetic acid Methyl, ethyl acetate, propyl acetate,
Soluble in low-boiling solvents such as butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, and methyl ethyl ketone to give alkylbenzene sulfonic acid and alkyl. Mixing with an aqueous solution containing an anionic surfactant such as naphthalene sulfonic acid and / or a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolauryl ester and / or a hydrophilic binder such as gelatin, and a high speed rotating mixer , Emulsified and dispersed by a colloid mill or an ultrasonic dispersion device and added to the silver halide emulsion.

In addition, the above-mentioned couplers and the like may be dispersed by using a latex dispersion method. The latex dispersion method and its effects are described in JP-A-49-74538, JP-A-51-59943, and JP-A-51-59943.
4-32552, Research Disclosure, August 1978, No. 14850, pp. 77-79.

Suitable latices include, for example, styrene, acrylates,
n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2- (methacryloyloxy) ethyltrimethylammonium methosulfate, 3- (methacryloyloxy) propane-1-sulfonic acid sodium salt, N-isopropylacrylamide,
Homopolymers, copolymers and terpolymers of monomers such as N- [2- (2-methyl-4-oxopentyl)] acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and the like.

The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives, for example, antifoggants, stabilizers, and ultraviolet absorbers described in Research Disclosure Magazine 17643. A color stain preventing agent, a fluorescent whitening agent, a color image fading preventing agent, an antistatic agent, a film hardening agent, a surfactant, a plasticizer, a wetting agent and the like can be used.

In the silver halide color photographic light-sensitive material of the present invention, hydrophilic colloids used for preparing emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxy. Any one of ethyl cellulose derivative, cellulose derivative such as carboxymethyl cellulose, starch derivative, single or copolymer synthetic hydrophilic polymer such as polyvinyl alcohol, polyvinyl imidazole, polyacrylamide and the like is included.

The support of the silver halide color photographic light-sensitive material of the present invention includes, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer, or in combination with a reflective material such as a glass plate and cellulose acetate. , Polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc., and other usual transparent supports may be used. These supports are appropriately selected according to the purpose of use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. Patent 2,761,791
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 2,941,898.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photographic light-sensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer from the support side. . Each of these light sensitive silver halide emulsion layers may consist of two or more layers. The effect of the present invention is great when all these photosensitive emulsion layers are substantially composed of silver chlorobromide emulsion.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and further, a filter layer,
Various layers such as an anti-curl layer, a protective layer and an antihalation layer can be appropriately combined and used as constituent layers. A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated.

EFFECTS OF THE INVENTION According to the present invention, even when the processing is performed with a low replenishing amount using a color developing solution, a constant and appropriate photographic performance is always maintained for a long time without being affected by a change in bromide ion concentration, and The developed coloring dye and undeveloped area do not change color or discolor even when stored for a long period of time, and cyan color contamination does not occur in the unexposed area. A method of processing a photographic light-sensitive material can be provided.

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

Example 1 On a polyethylene-laminated paper support, the following layers were sequentially coated from the support side to prepare silver halide color photographic light-sensitive material samples Nos. 1 to 25.

Layer 1 ... Gelatin of 1.2 g / m ² , blue-sensitive silver halide gelatin emulsion having a silver content of 0.30 g / m ² (in terms of silver, the same applies hereinafter) (silver halide composition and average grain size are shown in Table 1). .), 0.55g /
It was dissolved in m ² dioctyl phthalate. Blue-sensitive silver halide emulsion layer containing 0.80 g / m ² of yellow coupler (Y-1).

Layer 2 ... an intermediate layer consisting of 0.70 g / m ² of gelatin.

Layer 3 ... 1.25 g / m ² gelatin, green-sensitive silver halide gelatin emulsion having a silver content of 0.29 g / m ² (silver halide composition and average grain size are shown in Table 1), 0.35 g / m 0.62 g / m ² magenta coupler (M-1) dissolved in ² dioctyl phthalate
A green-sensitive silver halide emulsion layer containing

Layer 4 ... an intermediate layer consisting of 1.2 g / m ² of gelatin.

Layer 5: 1.4 g / m ² gelatin, red-sensitive silver halide gelatin emulsion having a silver content of 0.27 g / m ² (silver halide composition and average grain size are shown in Table 1), 0.25 g / m red-sensitive silver halide emulsion layer containing a ^second dioctyl phthalate dissolved 0.50 g / m ² of cyan coupler (compound C-8).

Layer 6 ... A protective layer containing 0.50 g / m ² of gelatin.

The silver halide of 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 used in which the color was increased by a general sensitizing dye.

(Y-1) (M-1) As a hardening agent, 2,4-dichloro-6-hydroxy-S-triazine sodium was added to layers 2, 4 and 6 so that the amount was 0.02 g per 1 g of gelatin, and after drying, the following color developing solution was added. The gelatin film swelling rate T1 / 2 was measured at 30 ° C. using a sol. For about 9 seconds. The measurement was performed using a Lebenzone type swelling meter.

Each of the photosensitive material sample Nos. 1 to 25 shown in Table 1 was exposed through an optical wedge and then processed in the next step.

Processing step (38 ° C) Color development 120 seconds Bleaching fixing 60 seconds Washing with water 60 seconds Drying 60 to 80 ° C 120 seconds The composition of each processing solution is as follows.

[Color developer] Pure water 800m Benzyl alcohol 15m 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) 6.0g 1-Hydroxye Tylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5m Magnesium chloride 0.3g Potassium carbonate 32g Kaycoll-PK- Conc (fluorescent brightener, manufactured by Shin Nisso Kako Co., Ltd.) 1.0 g Add pure water to make 1 and adjust the pH to 10.1 with 20% potassium hydroxide or 10% dilute sulfuric acid.

[Bleach-fixing solution] Pure water 550m Ethylenediaminetetraacetic acid Iron (III) ammonium salt 65g Ammonium thiosulfate (70% aqueous solution) 85g Sodium hydrogen sulfite 10g Sodium metabisulfite 2g Ethylenediaminetetraacetic acid-2sodium 20g Pure water is added to make 1 PH with ammonia water or dilute sulfuric acid
Adjust to 7.0.

Separately, the potassium bromide concentration of the above color developing solution is 0.6 g /
Each of the same sample Nos. 1 to 25 as described above was developed using color developing solutions which were different only in the amounts of 5 g / and 3.5 g /.

Sensitometry was performed on each of the obtained samples by a conventional method. When the potassium bromide concentration was 0.6 g /, the concentration of the exposed area near the concentration 1.0 of each sample was set to 100, and the movement of the concentration when the potassium bromide concentration was changed is shown in Table 1. Only the cyan density is shown in Table 1 as the ratio of color density.

Color developing agent for comparison [CD-3] [CD-6] As is clear from the results in Table 1, compared to Samples No. 1 to No. 12 in the case where the silver halide is not substantially silver chlorobromide,
Sample No. 13 to No. 25 in the case of substantially silver chlorobromide, the color developing agent is the exemplary compound (1) or
In the case of (2), the bromide ion concentration in the color developer is
It can be seen that there is little change in the color density even with changes of 0.6 g /, 1.5 g /, and 3.5 g /, indicating high processing stability.
On the other hand, the conventionally known color developing agent CD-3 or
In the case of CD-6, regardless of the composition of the silver halide, it is found that in any case, there is a drawback in that the color density decreases as the bromide ion concentration in the color developer increases. Since Table 1 shows that the amount of replenishment was smaller as the bromide ion concentration was higher, the amount of replenishment can be significantly reduced in the treatment of the present invention.

Example 2 The silver halide photographic light-sensitive material sample No. 21 of Example 1 was exposed to light, and the same processing solution and processing steps as in Example 1 and the following replenishing solution were used to produce different color developing agents (4 in Table 2). Seed) was continuously processed until the total replenishment amount of the color developing replenisher became twice the tank volume.

[Color development replenisher] Pure water 800m Benzyl alcohol 19m Hydroxyamine sulfate 3.0g Potassium sulfite 3.0g Triethanolamine 5.0g Color developing agent (as shown in Table 2) 8.0g 1-Hydroxyethylidene-1,1-diphos Phosphoric acid (60% aqueous solution) 1.7m Magnesium chloride 0.6g Potassium carbonate 32g Kaycoll-PK- Conc (fluorescent brightener, manufactured by Shin Nisso Kako Co., Ltd.) 2.0g Pure water is added to 1 Adjust the pH to 10.4 with 20% potassium hydroxide or 10% dilute sulfuric acid.

[Bleach-fixing replenisher] Example 1 and the bleach-fixing replenisher were adjusted to pH = 6.5 by finishing to 800 m.

The replenishment amount was 330 m for both the color developing replenisher and the bleach-fixing replenisher per 1 m ² of the light-sensitive material.

The photosensitive material sample No. 21 of Example 1 was exposed to light in the same manner as in Example 1, and the color developing temperature was changed to 38 ° C. using the processing solution after the above continuous processing, and the color developing time was changed as shown in Table 2. Let

The reflection density of the white background of the unexposed portion of the obtained sample was measured with a spectrophotometer (manufactured by Hitachi Ltd.) of 660 nm. The results are shown in Table 2. Then, the sample was stored under irradiation of a xenon lamp and the change in cyan density was measured. That is, at each processing time, when the sample initial density of 1.0 when CD-3 was used as the color developing agent deteriorated by about 0.3, the decrease in the density in the same density range of the sample processed with another color developing solution was measured. The results are shown in Table 2. At this time, the yellow stain density of the unexposed area of the same sample was measured with PDA-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.) and the results are shown in Table 2.
It was shown to.

As is clear from the results shown in Table 2, when the color developing solution used CD-3 or CD-6 as the color developing agent, the cyan color of the unexposed white background on the same day immediately after the color developing time was several seconds. No significant difference in stain concentration and fading rate was observed. Among them, it can be seen that compared to CD-3, CD-6 is larger in both cyan stain and fading on the same day. 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) or (2) of the present invention, when the color developing processing time is 180 seconds or more, the cyan stain on the same day is high and the fading is large and it cannot be put to practical use. This means that the yellow stain density (Dm
in).

However, it is understood that when the color development time is 150 seconds or less, cyan stain and storage stability on the same day are rapidly improved, and more preferable results are obtained as compared with the case of using the above CD-3. This is surprising from the fact that the structure of the color-forming dye has conventionally been closely related to the stability of the dye, and it is predicted that the residual amount of the color-developing agent in the film is also greatly related. It

Example 3 Using the silver halides of Samples No. 3 and No. 21 of Example 1, respectively, the silver coating amounts of the blue, green and red sensitive emulsion layers were the same as those of Example 1.
Samples with various amounts of hardener added were prepared by using the same amount of silver halide as the above. The dried sample was measured for the film swelling speed T1 / 2 by a Lebenzone swelling meter using the color developing solution (measurement processing temperature: 30 ° C.). The film swelling speed T1 / 2 is 2 seconds, 5 seconds, 10 seconds, 15 seconds, 30 seconds, 40 seconds,
The samples with 60 seconds, 90 seconds, and 120 seconds were selected and used in the experiment.
This sample was exposed to light in the same manner as in Example 1 and treated with the same treatment liquid as in Example 1. Table 3 shows the processing time (seconds) required for the maximum density to be 80 when the maximum density of cyan when color development was performed at 38 ° C. for 10 minutes was 100. This result shows the rapidity of the development completion point.

As is clear from the results in Table 3, when the silver halide is silver chlorobromide, the color developing agent is the present invention, and when the film swelling rate T1 / 2 is 30 seconds or less, the development is completed very quickly ( It shows that the rapid development processing is possible. On the other hand, even with the color developing agent of the present invention, the film swelling rate
When T1 / 2 is 40 seconds or more, the development completion (arrival) time becomes drastically long, and when the color developing agent is out of the present invention, fast development is possible even if the film swelling rate T1 / 2 is very small. No completion (arrival) time was obtained.

On the other hand, when the silver halide is substantially silver iodobromide, even if the color developing agent is that of the present invention, a fast development completion (arrival) time is obtained regardless of the length of the film swelling speed T1 / 2. It turns out that can't be obtained.

Example 4 Using the silver halide photographic light-sensitive materials of Samples No. 3 and No. 21 of Example 1, the blue, green and red sensitive emulsion layers had the same silver amount, and the total silver amount was 0.4 g / m ² , 0.75 g / m ² , 1.0 g / m ² , 2
Samples were prepared by coating so as to have g / m ² , 3 g / m ² , 5 g / m ² , and 7 g / m ² . Membrane swelling speed T1 / 2 of each sample (measurement processing temperature
(30 ° C.) was 7 seconds. The coupler is 1.0 g of the amount of Example 1.
It was used in the case of / m ² and others were created by changing the silver amount ratio. The processing solution used was the same as in Examples 1, 2, and 3 except that the color developing agent was changed.

The bromide ion concentration was 1.5 g / potassium bromide. When the color developing solution was color developed at 38 ° C. for 10 minutes, the maximum cyan density was set to 100, and the processing time (seconds) required for the maximum density to reach 80 was measured and shown in Table 4. As in Example 3, the development completion time is shown.

As is clear from the results in Table 4, even in the process of the present invention, the development completion time tends to increase sharply as the total silver amount increases, but the development completion time is significantly shorter than that in the comparative process. I understand.

Example 5 Sample No. 21 of Example 1 was used, and the amount of silver halide was adjusted so that the silver coating amounts of the blue, green and red sensitive emulsion layers were the same as in Example 1, and a cyan coupler was used for the following comparison. Instead of the couplers and the exemplified couplers of the present invention shown in Table 5, the addition amount of the hardener was changed in the same manner as in Example 3 to prepare samples having different film swelling rates. This sample was exposed in the same manner as in Example 1 to obtain a color developing solution using the exemplified compounds (1) and (2) of Example 2, which were converged by continuous treatment, and Processing was performed with the color developing solution at the start of the continuous processing shown. The maximum density of cyan at the time of color development at 38 ° C. for 10 minutes was set to 100, and the reflection density at 660 nm of the white background of the unexposed area when the maximum density was 80 was measured. The results are shown in Table 5.

[Comparative cyan coupler used in Table 5] Comparison (1) Comparison (2) As is clear from the results shown in Table 5, when the cyan coupler is a comparative coupler other than the present invention and the film swelling speed T1 / 2 is 30 seconds or less, the continuous processing of the color developer produces a reflection density (cyan stain) on a white background. 660 nm) becomes high, and it can be seen that it cannot be put to practical use for users who maintain development by replenishment using a general automatic developing machine.

On the other hand, it can be seen that the one using the cyan coupler of the present invention has a low reflection density (cyan stain 660 nm) on a white background, which is extremely preferable even in a color developer which is continuously processed.

[Brief description of drawings]

FIG. 1 is a graph showing the film swelling speed T1 / 2 of the binder.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhiro Kobayashi 1 Sakura-cho, Hino-shi, Tokyo Photo Konishi Roku Photo Industry Co., Ltd. (72) Masao Ishikawa 1 Sakura-cho, Hino-shi, Tokyo Photo Roku Konishi Photo Co., Ltd. In-house (56) References US Patent 3714992 (US, A) UK Patent 3342559 (GB, A)

Claims (11)

[Claims] 1. A method for developing a silver halide color photographic light-sensitive material, wherein the silver halide emulsion in at least one light-sensitive emulsion layer is substantially a silver chlorobromide emulsion, and the binder film swelling speed T1. / 2 is 30 seconds or less, a silver halide color photographic light-sensitive material containing a cyan coupler represented by the following general formula [I] in a red-sensitive emulsion layer, and an N-hydroxyalkyl-substituted-p-phenylenediamine derivative A method of processing a silver halide color photographic light-sensitive material, which comprises performing development processing at 30 ° C. or higher for 150 seconds or less using a color developer contained therein. General formula [I] In the formula, one of R and R ₁ is a hydrogen atom, and the other is at least a linear or branched alkyl group of 2 to 12, and X is a hydrogen atom or the N-hydroxyalkyl-substituted-p-phenylenediamine derivative It represents a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent, and R ₂ represents a ballast group. 2. The silver halide emulsion of at least one light-sensitive emulsion layer is a silver chlorobromide emulsion having a silver bromide content of 90 mol% or less. 5. A method for processing a silver halide color photographic light-sensitive material as described in the above item. 3. The silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the total silver coating amount of the silver halide color photographic light-sensitive material is 1 g / m ² or less. Processing method. 4. A silver halide color photographic light-sensitive material according to any one of claims 1 to 3, wherein the color developing solution contains at least 5 × 10 ^-3 mol of bromide. Processing method. 5. The method for processing a silver halide color photographic light-sensitive material according to claim 4, which comprises processing with a color developer containing 1 × 10 ^-2 mol or more of bromide. 6. A process according to claim 4, wherein the color developer is treated with a color developer containing 1.5 × 10 ^-2 mol or more of bromide.
5. A method for processing a silver halide color photographic light-sensitive material as described in the above item. 7. The processing of a silver halide color photographic light-sensitive material according to claim 1, wherein the film swelling speed T1 / 2 of the binder is 20 seconds or less. Method. 8. The method of processing a silver halide color photographic light-sensitive material according to claim 3, wherein the total coated silver amount is 0.8 g / m ² or less. 9. An N-hydroxyalkyl-substituted-p-phenylenediamine derivative is 3-methyl-4-amino-N-ethyl-N-β-
A method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 8, which is a hydroxyethylaniline salt. 10. The silver halide according to any one of claims 1 to 9, wherein the replenishing amount in the continuous processing of the color photographic light-sensitive material is 250 m / m ² or less. Color photographic light-sensitive material processing method. 11. The method for processing a silver halide color photographic light-sensitive material according to claim 10, wherein the replenishing amount in the continuous processing of the color photographic light-sensitive material is 200 m / m ² or less.