JPH0827522B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a processing method for developing and then desilvering an exposed silver halide color photographic light-sensitive material. The present invention relates to an improved processing method capable of stabilizing a processed image.

(Prior Art) Generally, the basic steps of processing a color light-sensitive material are a color development step and a desilvering step. In the color developing process, the silver halide exposed by the color developing agent is reduced to produce silver, and the oxidized color developing agent is a color developing agent (coupler).
To give a dye image. In the next desilvering step, the silver produced in the color development step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved by a complexing agent of silver ions, commonly known as a fixing agent. It Through this desilvering process, only the dye image is formed on the color light-sensitive material.

The above desilvering step is carried out in two baths of a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, and in a single bath of a bleaching fixing bath in which a bleaching agent and a fixing agent are coexistent. There is.

The actual development process includes various auxiliary steps such as to maintain the photographic and physical quality of an image or to improve the storability of an image, in addition to the above basic steps. For example, a hardening bath, a stopping bath, an image stabilizing bath, a washing bath and the like.

In recent years, with the spread of small in-store processing service systems called mini-labs, there has been a strong demand for shortening the time required for the above processing in order to quickly respond to processing requests from customers.

In particular, the shortening of the desilvering step, which conventionally occupies most of the processing time, has been the most requested.

However, the ethylenediaminetetraacetic acid ferric iron complex salt, which is a mainstream bleaching agent used in the bleaching solution and the bleach-fixing solution, has a basic drawback that its oxidizing power is weak,
Despite various improvements such as the combined use of a bleaching accelerator, the above requirements have not been satisfied.

On the other hand, red blood salts, dichromates, ferric chloride persulfates, bromates, etc. are known as bleaching agents with strong oxidizing power, but environmental protection, handling safety, metal corrosiveness, etc. In view of the above, each has many drawbacks and cannot be widely used for over-the-counter processing and the like.

Under these circumstances, the bleaching solution containing a ferric complex of 1,3-diaminopropanetetraacetic acid and having a pH of about 6 described in JP-A-62-222252 is compared with a bleaching solution containing a ferric complex of ethylenediaminetetraacetic acid. Although it has a high oxidizing power and enables more rapid silver bleaching, it has a drawback that when it is bleached directly without an intermediate bath after color development, color fogging called bleaching fog occurs.

Apart from this bleaching fog problem, processing with a shorter bleaching time with this bleaching solution may give rise to a new problem that a large increase in stain occurs during storage of the processed light-sensitive material. It was revealed.

On the other hand, among the acylacetanilide type yellow couplers, yellow couplers having a leaving group bonded with a nitrogen atom at the coupling position are known. For example,
48-66835, 60-166948, U.S. Pat.No. 3409439,
The couplers described in 3730722, 4443536 and 4617256 are known. Although these couplers are excellent in the hue of dyes and heat fastness, they have a drawback that yellow stain (color increase in the yellow minimum density portion) occurs after processing. That is, the color developing agent is liable to remain in the processed color photographic light-sensitive material. Particularly, when the desilvering step, which is a post-step of color development, and the washing and / or stabilizing step are accelerated, the yellow stain after the processing is increased. The occurrence was remarkable, and the solution was desired.

(Problems to be solved by the invention) When the desilvering time is shortened by using a bleaching agent having excellent bleaching power as described above, bleaching fog is apt to occur, and it is treated with rapid processing. At the same time, it is necessary to solve the problem that the amount of residual active ingredient increases and, as a result, the generation of stains in the processed photosensitive material is remarkable.

(Means for Solving Problems) As a result of various studies in order to solve the above problems, it has been found that the problems can be solved by the following processing methods. That is, the color photographic light-sensitive material containing at least one of the yellow couplers represented by the following general formula [I] is color-developed and then processed by replenishing the bleaching solution with 100 to 1000 ml per 1 m ² of the light-sensitive material. Liquid is 1,3-
A bleaching solution containing 0.2 mol / l or more of ferric diaminopropanetetraacetic acid complex salt and 1 to 10 mol% of ferric complex salt of 1,3-diaminopropanetetraacetic acid and having a pH of 3 to 5. A method of processing the color photographic light-sensitive material, comprising:

General formula [I] In the general formula [I], R ₁ is a tertiary alkyl group or an aryl group, R ₂ is a hydrogen atom, a halogen atom, an alkoxy group or an aryloxy group, and R ₃ is a halogen atom, an alkyl group, an aryl group, an alkoxy group, Alkoxycarbonyl group, aryloxycarbonyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group,
A ureido group or an alkoxycarbonylamino group, X
Is a nitrogen atom and represents a heterocyclic group bonded to the coupling active position of the yellow dye-forming coupler represented by the general formula [I], and l represents an integer of 0 to 4, respectively. However, when 1 is plural, R ₃ may be the same or different.

 The bleaching solution is described in detail below.

A ferric complex of 1,3-diaminopropanetetraacetic acid is used in the bleaching solution of the present invention.
The amount is 2 mol or more, preferably 0.25 mol or more, and particularly preferably 0.3 mol or more for speeding up. However, excessive use conversely inhibits the bleaching reaction, so 0.5 mol or less is preferable. The ferric complex of 1,3-diaminopropanetetraacetic acid is
Although ammonium salts such as sodium and potassium can be used, ammonium salts are preferred because they are the fastest in bleaching.
If the amount of the ferric complex salt of 1,3-diaminopropanetetraacetic acid is less than 0.2 mol, bleaching is rapidly delayed and stain after treatment increases, so that the present invention contains 0.2 mol or more. Is a condition.

 Next, the pH of the bleaching solution of the present invention will be described.

A pH 6 bleaching solution containing a ferric complex of 1,3-diaminopropanetetraacetic acid is known from JP-A-62-222252.
Conventionally, the pH of the bleaching solution containing ferric aminopolycarboxylic acid complex has been widely carried out around pH 6 from the standpoints of ensuring the bleaching speed and preventing the color restoration failure of the cyan dye. That is, although the bleaching speed is improved by lowering the pH, the color reversal failure of the cyan dye occurs, so that the optimum balance has been set at around pH 6.

On the other hand, the present invention has a characteristic that the effect is exhibited by setting the pH of the bleaching solution to 5.5 or less, and it is said to be contrary to the conventional art that rapid desilvering and complete color restoration of the cyan dye can be achieved. Solve the problem. Moreover, the problem of post-treatment color increase due to the yellow coupler could be solved. The pH of the bleaching solution of the present invention is 5.0 to 3.0, more preferably
It is 4.5 to 3.5. To adjust the pH to this region, acetic acid,
Organic acids such as citric acid, malonic acid, etc., and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid can be used, but acids having an acid dissociation index (pKa) in the range of 2.5 to 5.5 are buffered in the region of the present invention. Preferred in terms of imparting properties, in addition to the acetic acid, citric acid, malonic acid, benzoic acid, formic acid, butyric acid, malic acid, tartaric acid,
Various organic acids such as oxalic acid, propionic acid and phthalic acid can be mentioned. Of these, acetic acid is particularly preferred.

The amount of these acids used is preferably 0.1 to 2 mol, and particularly preferably 0.5 to 1.5 mol, per 1 bleaching solution.

It is preferable to add 1,3-diaminopropanetetraacetic acid to the bleaching solution in a slightly excess amount over the amount required for complex formation with ferric ion, and in the present invention, an excess amount is in the range of 1 to 10%. To do.

The bleaching solution of the present invention may contain a ferric complex of aminopolycarboxylic acid other than a ferric complex of 1,3-diaminopropanetetraacetic acid, and specifically, ethylenediaminetetraacetic acid and diethylenetriaminepentaferric acid. Acetic acid and a ferric complex salt of cyclohexanediaminetetraacetic acid can be given.

Various bleaching accelerators can be added to the bleaching solution of the present invention.

For such bleaching accelerators, for example, U.S. Patent No. 3,893,858, German Patent No. 1,290,812, British Patent No. 1,138,842, JP-A-53-95630, Research Disclosure No. 17129 (1978
Compounds having a mercapto group or a disulfide group described in JP-A No. 50-140129, thiourea derivatives described in US Pat. No. 3,706,561 and JP-A 58- The iodides described in 16235, the polyethylene oxides described in German Patent 2,748,430, and the polyamine compounds described in JP-B-45-8836 can be used. Particularly preferred are mercapto compounds as described in GB 1,138,842.

The bleaching solution constituting the present invention includes, in addition to the bleaching agent and the above-mentioned compounds, bromides such as potassium bromide, sodium bromide, ammonium bromide or chlorides such as rehalogenates such as potassium chloride, sodium chloride and ammonium chloride. Agents may be included. The concentration of the rehalogenating agent is 0.1 to 5 mol, preferably 0.5 to 3 mol, per 1 bleaching solution.

Moreover, it is preferable to use ammonium nitrate as a metal corrosion inhibitor.

The replenishing amount of the bleaching solution of the present invention is 100 ml to 1 m ² of the light-sensitive material.
It is 1000 ml.

In the treatment, the bleaching solution is preferably oxidized with ferrous 1,3-diaminopropanetetraacetic acid produced by aeration.

 The light-sensitive material after bleaching is then fixed.

As a fixing agent, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate; thiocyanates such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate; thiourea; thioether; it can.

Among them, ammonium thiosulfate is preferably used, and the amount thereof is 0.3 to 3 mol, preferably 1 mol of the fixing solution.
0.5 to 2 mol.

From the viewpoint of accelerating fixing, it is also preferable to use the above-mentioned ammonium thiocyanate (rhodanammonium), thiourea and thioether (for example, 3,6-dithia-1,8-octanediol) in combination. The amount is generally 0.01 mol to 0.1 mol per 1 fixing solution, but depending on the case, the use of 1 to 3 mol can greatly enhance the fixing promoting effect.

The fixing solution may contain a sulfite as a preservative, for example, sodium sulfite, potassium sulfite, ammonium sulfite, and a bisulfite adduct of hydroxylamine, hydrazine, and an aldehyde compound, for example, sodium acetaldehyde bisulfite. . Further, various optical brighteners and defoaming agents or surfactants, polyvinylpyrrolidone, it is possible to contain an organic solvent such as methanol, particularly as a preservative described in Japanese Patent Application No. 60-283831 It is preferable to use the sulfinic acid compound of.

From 300ml per photosensitive material 1 m ² as the replenishing amount of the fixing solution
3000ml is preferred, more preferably 300ml to 1000ml
Is.

Further, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution of the present invention for the purpose of stabilizing the solution.

The shorter the total time of the desilvering process of the present invention, the more remarkable the effect of the present invention can be obtained. The preferred time is 1 minute to 4 minutes, more preferably 1 minute 30 seconds to 3 minutes. The processing temperature is 25 °
-50 ° C, preferably 35 ° C-45 ° C. In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented.

In the desilvering process of the present invention, it is preferable that the stirring is strengthened as much as possible in order to more effectively exhibit the effects of the present invention.

As a specific method of strengthening stirring, JP-A-62-183460,
No. 62-183461, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material, a method of improving the stirring effect by using a rotating means of JP-A No. 62-183461, and further provided in the solution. Examples include a method of moving a light-sensitive material while bringing the wiper blade into contact with the emulsion surface to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the de-speed.

The means for improving the agitation is more effective when a bleaching accelerator is used, and can significantly increase the accelerating result or eliminate the fixing inhibition effect of the bleaching accelerator.

The automatic developing machine used in the present invention is disclosed in JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 191258 and 191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the fixed price of the performance of the treatment liquid. The effect is particularly effective in shortening the processing time in each step and reducing the replenishment amount of the processing liquid.

The effect of the present invention is remarkable when the total processing time is short. Specifically, the effect is clearly exhibited when the total processing time is 8 minutes or less. Will be noticeable. Therefore, in the present invention, the total processing time is preferably 8 minutes or less, particularly preferably 7 minutes or less.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, and representative examples thereof are shown below, but the invention is not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl -N-ethyl-N- [β
-(Methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino-3 -Methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N-β-
Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β-
Butoxyethylaniline Among the above p-phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferable.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent to be used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per developer.

Further, as a preservative, a sulfite salt such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct is added to the color developer as needed. be able to.

The preferable addition amount is 0.5 g to 10 g per color developer.
More preferably, it is 1 g to 5 g.

Further, as a compound that directly preserves the color developing agent, various hydroxylamines, hydroxamic acids described in Japanese Patent Application No. 61-186559, hydrazines described in 61-170756, and hydrazides, 61-188742. No. and No. 61-203253
No. 61-188741, α-hydroxyketones and α-aminoketones, and / or the same.
It is preferable to add various sugars described in No. 61-180616.
Further, in combination with the above compound, Japanese Patent Application Nos. 61-147823 and 61-
166674, 61-165621, 61-164515, 61-17078
No. 9, and monoamines described in No. 61-168159, etc., No. 61
-173595, 61-164515, 61-186560 and the like diamines, 61-165621, and 61-169789 polyamines described, 61-188619 polyamines described, 6
Nitroxy radicals described in 1-197760, 61-186561
, And alcohols described in 61-197419, 61-198987
It is preferable to use the oximes described in No. 61-265149 and the tertiary amines described in No. 61-265149.

Other preservatives include JP-A-57-44148 and 57-537.
Various metals described in No. 49, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349,
An aromatic polyhydroxy compound described in U.S. Pat. No. 3,746,544 may be contained as necessary. It is particularly preferable to add an aromatic polyhydroxy compound.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developing solution may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, o
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer is preferably 0.1 mol / l or more, and more preferably 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

As the chelating agent, an organic acid compound is preferable, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples are shown below, but the present invention is not limited thereto.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid,
1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphone Acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid,
Two or more of these chelating agents may be used in combination, if necessary.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g per unit.

If necessary, any development accelerator can be added to the color developing solution. However, it is preferred that the color developer of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation and prevention of color contamination. Here, “substantially” means that the amount of the developer is not more than 2 ml, preferably not contained at all.

Other development accelerators include JP-B-37-16088 and 37
No. 5987, No. 38-7826, No. 44-12380, No. 45-9019, and thioether compounds represented by U.S. Pat.No. 3,813,247, etc., and those described in JP-A Nos. 52-49829 and 50-15554. P-phenylenediamine compounds, disclosed in JP-A-50-13772
No. 6, JP-B-44-30074, JP-A-56-156826 and JP-A-52-4
Nos. 3,429, quaternary ammonium salts, U.S. Pat.Nos. 2,494,903, 3,128,182, 4,230,796,
3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat.No. 2,482,546
Nos. 2,596,926 and 3,582,346, etc., amine compounds, JP-B-37-16088, JP-B-42-25201, U.S. Pat.No. 3,128,183, JP-B-41-11431, 42-23883 and US If necessary, polyalkylene oxide represented by Japanese Patent No. 3,532,501 and the like, 1-phenyl-3-pyrazolidones, imidazoles and the like can be added.

In the present invention, any antifoggant can be added if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole and 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples thereof include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compound is preferable.
The addition amount is 0 to 5 g / l, preferably 0.1 g to 4 g / l.

If necessary, various surfactants such as alkylsulfonic acid, arylphosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The processing temperature of the color developing solution of the present invention is 20 to 50 ° C, preferably 30 to 45 ° C. Processing time is 20 seconds to 5 minutes, preferably 30
Seconds to 3 minutes. The replenishment amount is preferably smaller, but is preferably 100 to 1500 ml, preferably 100 to 800 ml, per m ^{2 of} the light-sensitive material.
More preferably, it is 100 ml to 400 ml.

Also, the color developing bath is divided into two or more baths as necessary,
Replenish the color developer replenisher from the last bath or the last bath,
The development time and the replenishment amount may be reduced.

The processing method of the present invention can also be used for color reversal processing. In the present invention, a so-called black-and-white first developing solution used for reversal processing of a color photographic light-sensitive material which is generally known as a black-and-white developing solution used at this time, or a solution used for processing a black-and-white photosensitive material can be used. In addition, various well-known additives generally added to a black-and-white developer can be contained.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, methol and hydroquinone, preservatives such as sulfites, and accelerators composed of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate. , Potassium bromide, 2-methylbenzimidazole,
Inorganic or organic inhibitors such as methylbenzthiazole, water softeners such as polyphosphates, trace amounts of iodides, and development inhibitors composed of mercapto compounds can be mentioned.

The processing method of the present invention comprises the above-described processing steps such as color development, bleaching, bleach-fixing and fixing. here,
After the bleach-fixing or fixing step, processing steps such as washing and stabilization are generally performed. However, after a bath having a fixing ability, a simple stabilization treatment without substantial washing is performed. Processing methods can also be used.

The washing water used in the washing step may contain known additives, if necessary. For example, hard water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, bactericides and antifungal agents that prevent the growth of various bacteria and algae (eg, isothiazolone, organochlorine bactericides, benzotriazole, etc.) , A drying load, and a surfactant for preventing unevenness can be used. Or L, E,
West, “Water Quality Criteria”, Phot.Sci.and Eng., V
ol. 9, No. 6, pages 344 to 359 (1965) and the like can also be used.

As the stabilizing solution used in the stabilizing step, a processing solution that stabilizes the dye image is used. For example, a liquid having a buffering capacity of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), and the like can be used. The stabilizing solution may contain, as necessary, a metal compound such as an ammonium compound, Bi, or Al, a fluorescent brightener, a chelating agent (eg, 1-hydroxyethylidene-1,1-diphosphonic acid), a bactericide, and a deodorant. , A hardener, a surfactant and the like can be used.

The washing step and the stabilizing step are preferably a multi-stage countercurrent system, and the number of stages is preferably 2 to 4. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times, the amount carried in from the previous bath per unit area.

The water used in these washing or stabilization processes include tap water, C
It is preferable to use deionized water having an a or Mg concentration of 5 mg / l or less, water sterilized by halogen, an ultraviolet sterilization lamp or the like.

In each of the above processing steps of the photosensitive material, when the continuous processing by the automatic developing machine is performed, the processing solution may be concentrated by evaporation, which is remarkable especially when the processing amount is small or the opening area of the processing solution is large. Becomes In order to correct such concentration of the treatment liquid, it is preferable to replenish an appropriate amount of water or the correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid of the washing process or the stabilizing process is caused to flow into a bath having a fixing ability as a pre-bath.

The yellow dye-forming coupler represented by formula (I) is described in detail below.

In the general formula [I], R ₁ preferably has 4 carbon atoms.
-30 represents an optionally substituted tertiary alkyl group or preferably an optionally substituted aryl group having 6 to 30 carbon atoms. When R ₁ represents a tertiary alkyl group, the substituent thereof may be a halogen atom (eg fluorine, chlorine, bromine, iodine), an alkoxy group (eg methoxy, ethoxy, methoxyethoxy, dodecyloxy), an aryloxy group (eg phenoxy). , P-methoxyphenoxy,
p-dodecyloxyphenoxy, p-methoxycarbonylphenoxy, m-chlorophenoxy), alkylthio group (eg methylthio, ethylthio, benzylthio, dodecylthio), arylthio group (eg phenylthio,
p-nitrophenylthio, p-dodecylphenylthio,
p-tolylthio), a sulfonyl group (for example, methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl), a sulfinyl group (for example, benzenesulfinyl, p-toluenesulfinyl, p-dodecylbenzenesulfinyl), a cyano group,
Thiocyanato group, hydroxy group, iodo group (eg phthalimide, succinimide), heterocyclic group (eg 1-pyrrolyl, 1-pyrazolyl, 1-imidazolyl, 1-benzimidazolyl, 3-hydantoinyl, morpholino, pyrrolidino, piperidino) and the like. . When R ₁ represents an aryl group, the substituent thereof is a halogen atom (eg, fluorine, chlorine, bromine, iodine), an alkyl group (eg, methyl, ethyl, i-propyl, sec-butyl, t-butyl, cyclohexyl). , Allyl, t-octyl, n-dodecyl, trifluoromethyl), alkoxy groups (eg methoxy, ethoxy, methoxyethoxy, n-tetradecyloxy, benzyloxy), nitro groups, amino groups (eg methylamino, diethylamino, pyrrolidyl). ), A carbonamide group (eg, acetamide, benzamide), a sulfonamide group (eg, methylsulfonamide, phenylsulfonamide, dodecylsulfonamide) and the like.

Examples of R ₁ include t-butyl group, 1,1-dimethylbutyl group, 1-methyl-1-ethylpropyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1-adamantyl group, 2-chloro- 1,1-dimethylethyl group,
2-phenoxy-1,1-dimethylethyl group, 2-phenylthio-1,1-dimethylethyl group, 2- (p-tolylsulfonyl) -1,1-dimethylethyl group, phenyl group, p
-Tolyl group, o-tolyl group, 4-chlorophenyl group, 2
-Chlorophenyl group, 4-nitrophenyl group, 3-nitrophenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 4-methoxy-
3- [2- (2,4-di-t-pentylphenoxy) butanamide] -phenyl group, 4-methoxy-3-methylsulfonamidophenyl group and the like.

In the general formula [I], R ₂ is a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, iodine), preferably an optionally substituted alkoxy group having 1 to 30 carbon atoms or 6 to 30 carbon atoms. Represents an aryloxy group. When R ₂ represents an alkoxy group, the substituent thereof is a halogen atom (eg, fluorine, chlorine, bromine, iodine), an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy,
n-butoxy, n-hexyloxy, n-octyloxy, 2-ethylhexyloxy, n-dodecyloxy,
n-tetradecyloxy, n-hexadecyloxy) and the like. When R ₂ represents an aryloxy group, its substituent is a halogen atom (for example, fluorine, chlorine, bromine,
Iodine), alkyl groups (eg methyl, ethyl, isopropyl, t-butyl), alkoxy groups (eg methoxy,
Ethoxy). Examples of R ₂ include a hydrogen atom and a halogen atom, as well as a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, a benzyloxy group, an n-tetradecyloxy group and a phenoxy group.

In the general formula [I], R ₃ is preferably a halogen atom (eg, fluorine, chlorine, bromine, iodine), having 1 to 1 carbon atoms.
30 alkyl group, 6 to 30 carbon atom aryl group, 1 to 30 carbon atom alkoxy group, 2 to 30 carbon atom alkoxycarbonyl group, 7 to 30 carbon atom aryloxycarbonyl group, carbon atom Carbonamido group having 1 to 30 carbon atoms, sulfonamide group having 1 to 30 carbon atoms, carbamoyl group having 1 to 30 carbon atoms, sulfamoyl group having 0 to 30 carbon atoms, alkylsulfonyl group having 1 to 30 carbon atoms ,
Represents an arylsulfonyl group having 6 to 30 carbon atoms, an ureido group having 1 to 30 carbon atoms or an alkoxycarbonylamino group having 2 to 30 carbon atoms, and when the above substituents contain an alkyl group, Is a halogen atom (eg fluorine, chlorine, bromine, iodine), a cyano group, a nitro group, an aryl group (eg phenyl, p-tolyl, 2-
Methoxyphenyl), alkoxy groups (eg methoxy,
Ethoxy, butoxy, benzyloxy, n-hexyloxy, 2-ethylhexyloxy, n-octyloxy, n-decyloxy, n-dodecyloxy, n-dodecyloxyethoxy, 2- (2,4-di-t-pentylphenoxy) ) Ethoxy], alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, n-butoxycarbonyl, n-dodecyloxycarbonyl), carbamoyl groups (eg N, N-dimethylcarbamoyl, N).
-Methyl-N-octadecylcarbamoyl, N-dodecyl-N-phenylcarbamoyl), an aryloxy group (for example, phenoxy, p-dodecyloxyphenoxy,
2,4-di-t-pentylphenoxy, p-t-octylphenoxy) and alkylthio groups, arylthio groups, sulfonyl groups, sulfinyl groups, imide groups, and heterocycles mentioned when R ₁ is a tertiary alkyl group. Group, etc., and when the above substituents contain an aryl group, the substituents include halogen atoms (eg fluorine, chlorine, bromine, iodine), alkyl groups (eg methyl, ethyl, i-propyl, aryl, benzyl). , T-butyl, sec-butyl, cyclopentyl, cyclohexyl, t-octyl, n-decyl,
n-dodecyl), aryl groups (eg phenyl, p-tolyl), alkoxy groups (eg methoxy, ethoxy, n
-Dodecyloxy), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl) and the like.

In the general formula [I], X represents a heterocyclic group bonded to the coupling active position with a nitrogen atom, and more specifically, these heterocycles are monocyclic or condensed heterocyclic 5 to 7-membered heterocyclic rings. A ring, examples of which are succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole,
Benzimidazole, benzotriazole, imidazolidin-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, imidazolin-2-one,
Oxazolin-2-one, thiazolin-2-one, benzimidazolin-2-one, benzoxazoline-2-
On, benzothiazolin-2-one, 2-pyrroline-5
-One, 2-imidazolin-5-one, indoline-2,
3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4
-Triazolidine-3,5-dione, 2-pyridone, 4-
There are pyridone, 2-pyrimidone, 6-pyridazone, 2-pyrazone, 2-amino-1,3,4-thiazolidine, 2-imino-1,3,4-thiazolidin-4-one, etc., and these heterocycles are It may be substituted. As the substituent, a halogen atom (for example, fluorine, chlorine, bromine, iodine), a hydroxy group, a nitro group, a cyano group, a carboxy group, a sulfo group, a carboxylate group, a sulfonate group, a sulfinate group, an alkyl group (for example, methyl, ethyl , N-decyl, t-butyl, trifluoromethyl, carboxymethyl), alkoxy groups (eg methoxy, ethoxy, methoxyethoxy), acyl groups (eg acetyl, benzoyl), alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, i). -Propoxycarbonyl, n-dodecyloxycarbonyl), a carbamoyl group (for example, N, N-dimethylcarbamoyl, N-methoxyethylcarbamoyl, N-tetradecylcarbamoyl),
A sulfonyl group (for example, a methanesulfonyl group, a benzenesulfonyl group, a 4-hydroxybenzenesulfonyl group),
A sulfamoyl group (for example, N-methylsulfamoyl,
N-phenylsulfamoyl, N-dodecylsulfamoyl), carbonamide group (eg acetamide, benzamide, trifluoroacetamide, pentafluorobenzamide), sulfonamide group (eg methanesulfonamide, p-toluenesulfonamide), amino Groups such as amino, N, N-dimethylamino, N, N-diethylamino, pyrrolidino, piperidino.

Next, the substituents preferably used in the present invention for each of the substituents R ₁ , R ₂ , R ₃ and X described above will be described.

R ₁ is preferably a t-butyl group, a phenyl group or a phenyl group substituted with a chlorine atom, a methyl group or a methoxy group, and more preferably a t-butyl group, a phenyl group or a 4-methoxyphenyl group.

R ₂ is preferably a chlorine atom or an alkoxy group having 1 to 8 carbon atoms, more preferably a chlorine atom or a methoxy group, and most preferably a chlorine atom.

R ₃ is preferably a halogen atom (for example, fluorine, chlorine,
Bromine, iodine), an alkoxy group (for example, methoxy, ethoxy, butoxy, methoxyethoxybenzyloxy, dodecyloxy, tetradecyloxy), an alkoxycarbonyl group (for example, ethoxycarbonyl, dodecyloxycarbonyl, (1-dodecyloxycarbonyl) ethoxycarbonyl, (1-dodecyloxycarbonyl) pentyloxycarbonyl], an aryloxycarbonyl group (for example, phenoxycarbonyl, 2,5-di-t-pentyl, phenoxycarbonyl), a carbonamide group [for example, acetamide, tetradecanamide, 2-hexyldecanamide, 2- (2,4-di-t-pentylphenoxy) butanamide, 4- (2,4-di-t-pentylphenoxy) butanamide, 3-dodecanesulfonyl-2-
Methylpropanamide, benzamide, 4-dodecyloxybenzamide], sulfonamide group (for example, methanesulfonamide, dodecanesulfonamide, hexadecanesulfonamide, N-methylhexadecanesulfonamide, benzenesulfonamide, toluenesulfonamide, 4-dodecylbenzenesulfone) Amide, 4-tetradecyloxybenzenesulfonamide), a carbamoyl group [for example, N-methylcarbamoyl, N, N-dihexylcarbamoyl, pyrrolidinocarbonyl, N-tetradecylcarbamoyl, N-phenylcarbamoyl, N- (4
-Tetradecyloxyphenyl) carbamoyl] or a sulfamoyl group (for example, N-methylsulfamoyl,
N-butylsulfamoyl, N-hexadecylsulfamoyl, piperidinosulfonyl, N, N-dioctylsulfamoyl, N-phenylsulfamoyl), more preferably an alkoxycarbonyl group, a carbonamide group or It is a sulfonamide group.

l is preferably an integer of 0 to 2, and more preferably 1.

X is preferably a group represented by the following general formula [II].

General formula (II) In the general formula [II], Z is Represents Here, R ₄ , R ₅ , R ₈ and R ₉ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a naralkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an amino group, R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an aryl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group, and R ₁₀ and R ₁₁
Represents a hydrogen atom, an alkyl group or an aryl group. R
₁₀ and R ₁₁ may form a benzene ring bonded to each other. R ₄ and R ₅ , R ₅ and R ₆ , R ₆ and R ₇ or R ₄ and R ₈ are bonded to each other to form a ring (for example, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine).
May be formed.

Among the heterocyclic groups represented by the general formula [II], a particularly preferred one is Z in the general formula [II]. Is a heterocyclic group.

The total number of carbon atoms in the heterocyclic group represented by the general formula [II] is 2 to 30, preferably 4 to 20.

Examples of the heterocyclic group represented by the general formula [II] are succinimide group, maleinimide group, phthalimido group, 1-
Methylimidazolidin-2,4-dione-3-yl group, 1
-Benzylimidazolidin-2,4-dione-3-yl group, 5,5-dimethyloxazolidin-2,4-dione-3-
Group, 5-methyl-5-propyloxazolidine-2,
4-dione-3-yl group, 5,5-dimethylthiazolidine-
2,4-dione-3-yl group, 5,5-dimethylimidazolidin-2,4-dione-3-yl group, 3-methylimidazolidintrione-1-yl group, 1,2,4-triazolidine-
3,5-dione-4-yl group, 1-methyl-2-phenyl-1,2,4-triazolidine-3,5-dione-4-yl group,
1-benzyl-2-phenyl-1,2,4-triazolidine-3,5-dione-4-yl group, 5-hexyloxy-1
-Methylimidazolidin-2,4-dione-3-yl group,
1-benzyl-5-ethoxyimidazolidin-2,4-dione-3-yl group, 1-benzyl-5-dodecyloxyimidazolidin-2,4-dione-3-yl group and the like.

The coupler represented by the general formula [I] has substituents R ₁ , X or In, a dimer or a multimer having a valence of two or more may be bonded to each other to form a dimer or a multimer.
In this case, the number of carbon atoms may be out of the specified range for each substituent.

Specific examples of the yellow dye-forming coupler represented by the general formula [I] are shown below, but the invention is not limited thereto.

Other examples of compounds and / or synthetic methods of these couplers represented by the general formula [I] are described, for example, in US Pat.
No. 3409439, No. 3730722, No. 3770445, No. 384
No. 2576, No. 3941601, No. 3973968, No. 3990896
No. 3998641 No. 4008086 No. 4012259 No.
No. 4022620, No. 4032347, No. 4046575, No. 4
No. 049458, No. 4057432, No. 4115121, No. 413395
No. 8, No. 4138263, No. 4138557, No. 4201584,
No. 4203768, No. 4206278, No. 4229577, No. 4
No.266019, No.4269936, No.4286053, No.428984
No. 7, No. 4288591, No. 4238564, No. 4248961,
No. 4289847, No. 4304845, No. 4314023, No. 4
326024, 4327175, 4336327, 435625
No. 8, No. 4404274, No. 4443536, No. 4617256,
UK Patent No. 1580999, 2011398, West German Patent No. 3107
No. 173, European Patent Application (EP) No. 30747, JP-A-48-66835
No. 48-99432, No. 50-108925, No. 50-132926, No.
50-158329, 51-3631, 51-145319, 52-5892
No. 2, No. 52-115219, No. 54-121126, No. 55-538, No. 5
5-598, 55-93153, 55-163538, 56-30126
Issue 56-30127, Issue 56-74250, Issue 56-92539, Issue 56
-153343, 56-161543, 56-164343, 57-2223
No. 8, No. 57-155538, No. 58-21738, No. 58-42046, No.
59-159163, 59-222837, 60-35730, 60-144
No. 740, No. 60-166948 and Research Disclosure Magazine (R
D) No. 18053 (1979).

The addition amount of the yellow coupler of the present invention is 0.01 to 20 milmol, more preferably 0.1 to 5 per m ^{2 of the} color photographic light-sensitive material.
It is about millimolar.

The yellow coupler of the present invention may be used in any of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, but it is generally used in a blue-sensitive emulsion layer. Further, it may be used in any of the high sensitivity layer, the low sensitivity layer and the medium sensitivity layer.

The light-sensitive material of the present invention comprises at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support.
The number of layers and the layer order of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited as long as the layers are provided. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched in the same color-sensitive layer.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer, JP 61-43748, 59-113438,
No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler as described in the specification, DIR compounds and the like, and contains a color mixing inhibitor as is commonly used. Good.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of high-speed emulsion layer and low-speed emulsion layer as described in No.
A layer structure can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. In addition, JP-A-57-112751 and 62-20
As described in 0350, 62-206541, 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / B
It can be installed in the order of L / GL / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Also, as described in Japanese Patent Publication No. 55-34932,
It is also possible to arrange in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. In addition, JP-A-56-25738 and 62
It is also possible to arrange in order of the blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification of No. 63936.

Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. An arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and three layers having different sensitivities are sequentially reduced in sensitivity toward a support, may be mentioned. Even in the case of being composed of three layers having different sensitivities as described above, JP-A-59-202
As described in Japanese Patent No. 464, the medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side distant from the support in the same color-sensitive layer.

As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

Preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may have a regular crystal such as a tetradecahedron, an irregular crystal form such as a sphere or a plate, a crystal defect such as a twin plane, or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 17643 (1978.
December), pp. 22-23, "I. Emulsion preparati
on and types) ”, and No. 18716 (November 1979),
648, Graphide, "Physics and Chemistry of Photography", published by Paul Montel (P.Glafkides, Chemic et Phisique Photogr
aphique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographi
c Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (VLZelikman et al., Making and Coating Photo
It can be prepared using the method described in Graphic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineerin.
g), 14: 248-257 (1970); U.S. Pat. No. 4,434,2
No. 26, No. 4,414,310, No. 4,433,048, No. 4,439,520, and British Patent No. 2,112,157, and the like can be easily prepared.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide.

 Also, a mixture of particles having various crystal forms may be used.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat. No. 4,411,987 and 4,435,503
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde described in No.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in Research Disclosure (RD) No. 17643, VII-C to G mentioned above.

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat.
Those described in 968, 4,314,023, 4,511,619, European Patent 249,473A, and the like are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
619, 4,351,897, European Patent 73,636, U.S. Patents 3,061,432, 3,725,064, Research Disclosure No. 2422 (June 1984), JP-A-60-33552.
Issue, Research Disclosure No. 24230 (June 1984
Mon), JP-A-60-43659, 61-72238, 60-35730
No. 55-118034, No. 60-185951, U.S. Pat.No. 4,500,
No. 630, No. 4,540,654, No. 4,556,630, WO (PCT)
Those described in 88/04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200.
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2, No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453.
A, U.S. Pat.Nos. 3,446,622, 4,333,999, and
4,753,871, No. 4,451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212, No. 4,296,199,
Those described in JP-A-61-242658 and the like are preferable.

Colored couplers to correct unwanted absorption of colored dyes are Research Disclosure No. 17643 VII-
Paragraph G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent Nos. 4,004,929, 4,138,258, and British Patent 1,14.
Those described in 6,368 are preferred.

As a coupler in which the coloring dye has an appropriate diffusibility,
Those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570 and West German Patent (Publication) No. 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, 4,576,910, British Patent 2,10
2, 173, etc.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, VII-F above.
Patents described in paragraphs, JP-A-57-151944 and 57-154234
No. 60-184248, No. 63-37346, U.S. Patent No. 4,248,962
Those described in No. 10 are preferable.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,1.
Those described in 31,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472, and 4,338,393,
Multi-equivalent couplers described in JP-A No. 4,310,618 and the like, JP-A-60-
185950, DIR redox compound releasing coupler described in JP-A-62-24252, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173,302A, color recovery after separation. Coupler, R, D, No.11449, which releases dye
No. 24241, a bleaching accelerator releasing coupler described in JP-A No. 61-201247, a ligand releasing coupler described in U.S. Pat. No. 4,553,477, a coupler releasing a leuco dye described in JP-A-63-75747, etc. Is mentioned.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid ester Kinds (trifel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-
2-ethylhexyl phenylphosphonate, etc., benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecane amide, N, N-diethyllaurylamide) , N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert.
-Amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl- 2-butoxy-5-ter
t-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-hexane. Ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Suitable supports that can be used in the present invention are, for example, those mentioned above.
RD.No. 17643, page 28, and RD.No. 18716, page 647 From the right column
See page 648, left column.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, and the film swelling speed T1 / 2 is preferably 30 seconds or less. Film thickness is 25 ° C and relative humidity is 55%
Means the film thickness measured under humidity control (2 days), and the film swelling rate T1
/ 2 can be measured according to a method known in the art. For example, a swellometer (swelling meter) of the type described in Photographic Science and Engineering (Pho.Sci.Eng.), Volume 19, No. 2, pp. 124-129 by A. Green et al. T1 / 2 can be measured by using, and 90% of the maximum swollen film thickness reached when processed at 30 ° C for 3 minutes and 15 seconds with a color developer is taken as the saturated film thickness, and the film thickness of T1 / 2 is reached. It is defined as the time to do.

The film swelling speed T1 / 2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating.

The swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the above-mentioned conditions according to the following formula (maximum swelling film thickness-film thickness) / film thickness.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.No.
17643, pages 28-29, and No. 18716, 615, left column to right column, the development can be carried out by a usual method.

The color developer used for the development processing of the light-sensitive material of the present invention,
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent, but p-
A phenylenediamine compound is preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl-4-amino-N-ethyl-N-.
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples thereof include methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Fogging agent such as sodium boron hydride, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid , Hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-diene (O-Hydroxyphenylacetic acid) and their salts can be mentioned as representative examples.

When the reversal process is performed, black and white development is usually performed before color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a color developing agent at a high concentration.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (IV) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether amine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,98.
8, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418
No. 53, No. 53-72623, No. 53-95630, No. 53-95631, No. 53
-104232, 53-124424, 53-141623, 53-2842
No. 6, Research Disclosure No. 17129 (1978
Compounds having a mercapto group or a disulfide group described in JP-A No. 50-140129; JP-B-45-8506; JP-A-52-20832;
No. 53-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715, iodide salts described in JP 58-16,235; West German Patent Nos. 966,410, 2,748,430
Compounds described in Japanese Patent Publication No. 45-883
No. 6, polyamine compound; Others, JP-A-49-42,434
No. 49, 59-644, 53-94,927, 54-35,727,
The compounds described in Nos. 55-26,506 and 58-163,940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,8858 and West Patent 1,29.
Compounds described in JP-A No. 0,812 and JP-A No. 53-95,630 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but the use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), the purpose, and the rinsing water temperature.
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment system such as countercurrent and forward flow, and various other conditions. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in Japanese Patent Application No. 62-288,838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to
9, and preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilizing process, the method disclosed in
All known methods described in Nos. 57-8543, 58-14834, and 60-220345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat. Examples thereof include salt complexes and urethane compounds described in JP-A-53-135628.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64339, JP-A-57-144547, and JP-A-58-1154.
No. 38 etc. are described.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

Further, the silver halide light-sensitive material of the present invention is described in US Pat.
500,626, JP-A-60-133449, 59-218443, 61-
It can also be applied to the photothermographic materials described in 238056 and European Patent 210,660A2.

Example 1 On a cellulose triacetate film support having an undercoat, each layer having the following composition was applied in a multi-layered manner to prepare a sample 101 as a multilayer color photosensitive material.

(Photosensitive Layer Composition) The numbers corresponding to the respective components indicate the coating amount in g / m ² unit, and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver 0.18 Gelatin 0.40 Second layer (intermediate layer) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 Sensitizing dye I 6.9 × 10 ^-5 Sensitizing dye II 1.8 × 10 ^-5 Sensitizing dye III 3.1 × 10 ^-4 EX-2 0.335 EX-10 0.020 Gelatin 0.87 Fourth layer (second red-sensitive emulsion layer) Emulsion C Silver 1.0 Sensitizing dye I 5.1 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.3 × 10 ^-4 EX-2 0.400 EX-3 0.050 EX-10 0.015 Gelatin 1.30 Fifth layer (third red-sensitive emulsion layer) Emulsion D Silver 1.60 sensitization Sensitizing dye I 5.4 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.4 × 10 ^-4 EX-3 0.010 EX-4 0.080 EX-2 0.097 HSB-1 0.22 HSB-2 0.10 Gelatin 1.63 6th Layer (Intermediate layer) EX-5 0.040 HBS-1 0.020 Gelatin 0.80 7th layer (1st green emulsion layer) Emulsion A Silver 0. 15 Emulsion B Silver 0.15 Sensitizing dye V 3.0 × 10 ^-5 Sensitizing dye VI 1.0 × 10 ^-4 Sensitizing dye VII 3.8 × 10 ^-4 EX-6 0.260 EX-1 0.021 EX-7 0.030 EX-8 0.025 HBS- 1 0.100 HBS-3 0.010 Gelatin 0.63 8th layer (second green emulsion layer) Emulsion C Silver 0.45 Sensitizing dye V 2.1 × 10 ^-5 Sensitizing dye VI 7.0 × 10 ^-5 Sensitizing dye VII 2.6 × 10 ^-4 EX-6 0.094 EX-8 0.018 EX-7 0.026 HBS-1 0.160 HBS-3 0.008 Gelatin 0.50 9th layer (3rd green emulsion layer) Emulsion E Silver 1.2 Sensitizing dye V 3.5 × 10 ^-5 Sensitizing dye VI 8.0 × 10 ^-5 Sensitizing dye VII 3.0 × 10 ^-4 EX-13 0.015 EX-11 0.100 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54 10th layer (yellow filter layer) Yellow colloidal silver Silver 0.05 EX -5 0.08 HBS-1 0.03 Gelatin 0.95 11th layer (1st blue sensitive emulsion layer) Emulsion A Silver 0.08 Emulsion B Silver 0.07 Emulsion F Silver 0.07 Sensitizing dye VIII 3.5 × 10 ^-4 EX-9 0.721 EX-8 0.042 HBS -1 0.28 Gelatin 1.10 12th layer (second blue emulsion layer) Emulsion G Silver 0.45 Sensitizing dye VIII 2.1 × 10 ^-4 EX-9 0.154 EX-10 0.007 HBS- 1 0.05 Gelatin 0.78 13th layer (3rd blue-sensitive emulsion layer) Emulsion H Silver 0.77 Sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 Gelatin 0.69 14th layer (1st protective layer) Emulsion I Silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.05 Gelatin 1.00 15th layer (2nd protective layer) Polymethyl acrylate particles (diameter about 1.5 μm) 0.54 S-1 0.20 Gelatin 1.20 In addition to the above components in each layer , Gelatin hardener H-1 and surfactant were added.

HBS-1 tricresyl phosphate HBS-2 di-n-butyl phthalate The sample obtained as described above was designated as Sample 101. Next, Samples 102 to 106 were prepared in the same manner except that the yellow coupler EX-9 of the 11th layer, the 12th layer and the 13th layer of Sample 101 were changed to have equimolar amounts as shown in Table 1.

The following couplers were used as comparative yellow couplers.

The color light-sensitive material produced as described above was processed by using an automatic processor using the following processing steps and processing solutions.

(Stabilizer) Mother liquor and replenisher common Formalin (37%) 1.2 ml 5-chloro-2-methyl-4-isothiazolin-3-one 6.0 mg 2-methyl-4-isothiazolin-3-one 3.0 mg Surfactant 0.4 [ _{C 10 H 21 -OCH 2 CH 2} O 10 H ethylene glycol 1.0
1.0 l pH 5.7-7.0 by adding water First, the light-sensitive materials 101 to 106 were cut into a width of 35 mm, and a standard exposure was given to the inside of the camera. Treat this for 500 m to make each solution a steady running solution, add ammonia water and acetic acid to the bleaching solution, and change the pH of the bleaching solution as follows.
The running liquid of the conditions was prepared.

For each running solution obtained as described above, the samples 101 to 106 were passed through a wedge wedge to obtain 10 CMS.
After exposure.

Also, the minimum yellow density (D _B min) was measured immediately after the treatment, and then the sample was allowed to stand at 80 ° C. for 10 days, and the increase in yellow minimum density (ΔD _B min) was measured again.

 The results are shown in Table 1.

Samples 101 to 104 of the present invention has a small D _B min after treatment, yet increasing color with time was small. And especially for bleach
It is especially noticeable when the pH is between 2.5 and 5.5. increasing color after aging at pH2 is relatively small immediately after the processing D _B min is high,
It was found that this was due to desilvering failure.

The addition amount of ferric 1,3-diaminopropanetetraacetic acid ferric salt and 1,3-diaminopropanetetraacetic acid in the bleaching solution was reduced to 50% for both the mother liquor and the replenisher, and the pH was adjusted to 4.8. using the what, where the samples 101 to 106 were processed in the same manner as described above in step, all samples have high D _B min, and place significant desilvering defect, be a practical problem is indicated.

From the above, processing the color light-sensitive material containing the coupler constituting the present invention with the bleaching solution constituting the present invention, the stain after the treatment is small, the increase in color over time is small, and the desilvering failure is also small. Proved to be excellent.

Example 2 A sample 201, which is a multi-layer color light-sensitive material consisting of each layer having the composition shown below, was prepared on an undercoated cellulose triacetate film support.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer. The symbols indicating additives have the following meanings. However, when there are multiple utilities, one of them is listed as a representative.

UV; UV absorber, Solv; high boiling organic solvent, ExF; dye,
ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd; Additive first layer (antihalation layer) Black colloidal silver 0.15 Gelatin 2.9 UV-1 0.03 UV-2 0.06 UV-3 0.07 Solv-2 0.08 ExF-1 0.01 ExF-2 0.01 Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, spherical equivalent diameter 0.4 μ)
m, coefficient of variation of equivalent spherical diameter 37%, plate-like particles, diameter / thickness ratio
3.0) Silver coating amount 0.4 Gelatin 0.8 ExS-1 2.3 × 10 ^-4 ExS-2 1.4 × 10 ^-4 ExS-5 2.3 × 10 ^-4 ExS-7 8.0 × 10 ^-6 ExC-1 0.17 ExC-2 0.03 ExC- 3 0.13 Third layer (medium-speed red emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1 internal high A)
gI type, equivalent sphere diameter 0.65 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter / thickness ratio 2.0) Silver coating amount 0.65 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter 0.4) μ
m, coefficient of variation of equivalent spherical diameter 37%, plate-like particles, diameter / thickness ratio
3.0) Silver coating amount 0.1 Gelatin 1.0 ExS-1 2 × 10 ^-4 ExS-2 1.2 × 10 ^-4 ExS-5 2 × 10 ^-4 ExS-7 7 × 10 ^-6 ExC-1 0.31 ExC-2 0.01 ExC- 3 0.06 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1 internal high A)
gI type, equivalent sphere diameter 0.7 μm, variation coefficient of equivalent sphere diameter 25%, plate-like particles, diameter / thickness ratio 2.5) Coating silver amount 0.9 Gelatin 0.8 ExS-1 1.6 × 10 ^-4 ExS-2 1.6 × 10 ^-4 ExS-5 1.6 × 10 ^-4 ExS-7 6 × 10 ^-4 ExC-1 0.07 ExC-4 0.05 Solv-1 0.07 Solv-2 0.20 Cpd-7 4.6 × 10 ^-4 Fifth layer (intermediate layer) Gelatin 0.6 UV -4 0.03 UV-5 0.04 Cpd-1 0.1 Polyethyl acrylate latex 0.08 Solv-1 0.05 6th layer (low sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.4 μ)
m, coefficient of variation of equivalent spherical diameter 37%, plate-like particles, diameter / thickness ratio
2.0) Silver coating amount 0.18 Gelatin 0.4 ExS-3 2 × 10 ^-4 ExS-4 7 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-5 0.11 ExM-7 0.03 ExY-8 0.01 Solv-1 0.09 Solv- 4 0.01 7th layer (intermediate green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core-shell ratio 1: 1 surface height A
gI type, equivalent sphere diameter 0.5 μm, variation coefficient of equivalent sphere diameter 20%, plate-shaped particles, diameter / thickness ratio 4.0) Coating silver amount 0.27 Gelatin 0.6 ExS-3 2 × 10 ^-4 ExS-4 7 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-5 0.17 ExM-7 0.04 ExY-8 0.02 Solv-1 0.14 Solv-4 0.02 8th layer (high sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 8.7 mol%) , A multi-layer structure grain having a silver content ratio of 3: 4: 2, AgI content from the inside of 24 mol, 0 mol, 3 mol%,
Equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter / thickness ratio 1, 6) Coating silver amount 0.7 Gelatin 0.8 ExS-4 5.2 × 10 ^-4 ExS-5 1 × 10 ^-4 ExS -8 0.3 × 10 ^-4 ExM-5 0.1 ExM-6 0.03 ExY-8 0.02 ExC-1 0.02 ExC-4 0.01 Solv-1 0.25 Solv-2 0.06 Solv-4 0.01 Cpd-7 1 × 10 ^-4 9th layer (Intermediate layer) Gelatin 0.6 Cpd-1 0.04 Polyethyl acrylate latex 0.12 Solv-1 0.02 10th layer (donor layer of multi-layer effect for red-sensitive layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1 inside) High A
gI type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter / thickness ratio 2.0) Silver coating amount 0.68 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter 0.4) μ
m, coefficient of variation of equivalent spherical diameter 37%, plate-like particles, diameter / thickness ratio
3.0) Coating amount 0.19 Gelatin 1.0 ExS-3 6 × 10 ^-4 ExM-10 0.19 Solv-1 0.20 11th layer (yellow filter layer) Yellow colloidal silver 0.06 Gelatin 0.8 Cpd-2 0.13 Solv-1 0.13 Cpd-1 0.07 Cpd-6 0.002 H-1 0.13 12th layer (low sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, equivalent spherical diameter 0.7)
μm, coefficient of variation of equivalent sphere diameter 15%, tabular grain, diameter / thickness ratio 7.0) Coating silver amount 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3 μ)
m, coefficient of variation of equivalent sphere diameter 30%, plate-like particles, diameter / thickness ratio
7.0) Silver coating amount 0.15 Gelatin 1.8 ExS-6 9 × 10 ^-4 ExC-1 0.06 ExC-4 0.03 ExY-9 0.14 ExY-11 0.89 Solv-1 0.42 13th layer (intermediate layer) Gelatin 0.7 ExY-12 0.20 Solv -1 0.34 Layer 14 (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, spherical equivalent diameter 1.
0 μm, coefficient of variation of equivalent spherical diameter 25%, multiple twin plate-like particles,
Diameter / thickness ratio 2.0) Coating silver amount 0.5 Gelatin 0.5 ExS-6 1 × 10 ^-4 ExY-9 0.01 ExY-11 0.20 ExC-1 0.02 Solv-1 0.10 15th layer (1st protective layer) Fine grain silver iodobromide Emulsion (AgI 2 mol%, uniform AgI type, equivalent spherical diameter 0.07 μm) Silver coating amount 0.12 Gelatin 0.9 UV-4 0.11 UV-5 0.16 Solv-5 0.02 H-1 0.13 Cpd-5 0.10 Polyethyl acrylate latex 0.09 16th layer (Second protective layer) Fine grain silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Coating silver amount 0.36 Gelatin 0.55 Polymethylmethacrylate particles (diameter 1.5 μm) 0.2 H-1 0.17 For each layer In addition to the above ingredients, emulsion stabilizer Cpd-3
(0.07 g / m ² ) and a surfactant Cpd-4 (0.03 g / m ² ) were added as coating aids.

Solv-1 Tricresyl phosphate Solv-2 Dibutyl phthalate Solv-5 Trihexyl phosphate The color light-sensitive material produced as described above was processed with the following processing steps and processing solutions by using an automatic processor as in Example-1.

(Tap water) Mother liquor and replenisher common Tap water mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400) Water was passed through the bed-type column to treat calcium and magnesium ions at a concentration of 3 mg / l or less, and then 20 mg / l sodium diisocyanurate dichloride and 0.15 g / l sodium sulfate were added.

 The pH of this solution was in the range 6.5-7.5.

Sample 201 In D _B min is low, increase with time color also be very small proved.

Example 3 Sample 301, which is a multi-layer color light-sensitive material having each layer having the composition shown below, was prepared on an undercoated cellulose triacetate film support.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver 0.2 Gelatin 1.3 ExM-8 0.06 UV-1 0.1 UV-2 0.2 Solv-1 0.01 Solv-2 0.01 2nd layer (intermediate layer) Fine silver bromide (average particle size 0.07) μm) 0.10 Gelatin 1.5 UV-1 0.06 UV-2 0.03 ExC-2 0.02 ExF-1 0.004 Solv-1 0.1 Solv-2 0.09 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, Internal high AgI type, sphere equivalent diameter 0.3
μm, variation coefficient of equivalent spherical diameter 29%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 2.5) Coating silver amount 0.4 Gelatin 0.6 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1 × 10 ^-5 ExC-3 0.06 ExC-4 0.06 ExC-7 0.04 ExC-2 0.03 Solv-1 0.03 Solv-3 0.012 4th layer (second red emulsion layer) Silver iodobromide emulsion (AgI 5 mol%, Internal high AgI type, sphere equivalent diameter 0.7
μm, coefficient of variation of equivalent spherical diameter 25%, normal crystal, twin mixed particles, diameter / thickness ratio 4) Coating silver amount 0.7 Gelatin 0.5 ExS-1 1 × 10 ^-4 ExS-2 3 × 10 ^-4 ExS-3 1 × 10 ^-5 ExC-3 0.24 ExC-4 0.24 ExC-7 0.04 ExC-2 0.04 Solv-1 0.15 Solv-3 0.02 Fifth layer (third red emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, Internal high AgI type, sphere equivalent diameter 0.
8 μm, coefficient of variation of sphere equivalent diameter 16%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 1.3) Coating silver amount 1.0 Gelatin 1.0 ExS-1 1 × 10 ^-4 ExS-2 3 × 10 ^-4 ExS-3 1 × 10 ^-5 ExC-5 0.05 ExC-6 0.1 Solv-1 0.01 Solv-2 0.05 6th layer (intermediate layer) Gelatin 1.0 Cpd-1 0.03 Solv-1 0.05 7th layer (1st green emulsion layer) Iodine Silver bromide emulsion (AgI 2 mol%, internal high AgI type, spherical equivalent diameter 0.3
μm, variation coefficient of equivalent spherical diameter 28%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 2.5) Coating silver amount 0.30 ExS-4 5 × 10 ^-4 ExS-6 0.3 × 10 ^-4 ExS-5 2 × 10 ^-4 Gelatin 1.0 ExM-9 0.2 ExY-14 0.03 ExM-8 0.03 Solv-1 0.5 Eighth layer (second green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent spherical diameter) 0.6
μm, variation coefficient of equivalent spherical diameter 38%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 4) Coating silver amount 0.4 Gelatin 0.5 ExS-4 5 × 10 ^-4 ExS-5 2 × 10 ^-4 ExS-6 0.3 × 10 ^-4 ExM-9 0.25 ExM-8 0.03 ExM-10 0.015 ExY-14 0.01 Solv-1 0.2 9th layer (3rd green emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type) , Sphere equivalent diameter 1.0
μm, coefficient of variation of equivalent spherical diameter 80%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 1.2) Coating silver amount 0.85 Gelatin 1.0 ExS-7 3.5 × 10 ^-4 ExS-8 1.4 × 10 ^-4 ExM-11 0.01 ExM-12 0.03 ExM-13 0.20 ExM-8 0.02 ExY-15 0.02 Solv-1 0.20 Solv-2 0.05 10th layer (yellow filter layer) Gelatin 1.2 Yellow colloidal silver 0.08 Cpd-2 0.1 Solv-1 0.3 11th layer (First blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, spherical equivalent diameter 0.5)
μm, variation coefficient of spherical equivalent diameter 15%, octahedral grain) Coating silver amount 0.4 Gelatin 1.0 ExS-9 2 × 10 ^-4 ExY-16 0.9 ExY-14 0.07 Solv-1 0.2 12th layer (2nd blue-sensitive emulsion) Layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, spherical equivalent diameter 1.
3 μm, variation coefficient of equivalent spherical diameter 25%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 4.5) Coating silver amount 0.5 Gelatin 0.6 ExS-9 1 × 10 ^-4 ExY-16 0.25 Solv-1 0.07 13th layer (First protective layer) Gelatin 0.8 UV-1 0.1 UV-2 0.2 Solv-1 0.01 Solv-2 0.01 14th layer (Second protective layer) Fine grain silver bromide (average particle size 0.07 μm) 0.5 Gelatin 0.45 Polymethylmethacrylate Particles (diameter 1.5 μm) 0.2 H-1 0.4 Cpd-3 0.5 Cpd-4 0.5 In addition to the above components, a surfactant was added to each layer as a coating aid. Sample 10 was prepared as described above.
I set it to 1.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

Solv-1: Tricresyl phosphate Solv-2: Dibutyl phthalate Solv-3: Bis (2-ethylhexyl) phthalate The color light-sensitive material produced as described above was processed using an automatic developing machine in the same manner as in Example-1. By the treatment with the bleaching solution of the present invention, it was found that the sample 301 of the present invention had a small post-treatment yellow stain and an extremely small color increase.

Example 4 A multilayer color light-sensitive material 401 was produced by applying multiple layers of the following composition on a subbed cellulose triacetate film support.

(Photosensitive layer composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² unit, and the silver halide and colloidal silver indicate the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver 0.2 Gelatin 2.6 Cpd-3 0.2 Solv-1 0.02 Second layer (intermediate layer) Fine grain silver bromide (average particle size 0.07 μm) 0.15 Gelatin 1.0 Third layer (low sensitivity red) Emulsion-sensitive layer) Monodisperse silver iodobromide emulsion (5.5 mol% silver iodide, average grain size 0.3μ)
m, variation coefficient related to particle size (hereinafter simply referred to as variation coefficient) 19
%) 1.5 Gelatin 3.0 ExS-1 2.0 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 0.3 × 10 ^-4 ExC-1 0.7 ExC-2 0.1 ExC-3 0.02 Cpd-1 0.01 Solv-1 0.8 Solv -2 0.2 Solv-4 0.1 4th layer (high-sensitivity red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (3.5 mol% silver iodide, average grain size 0.7μ)
m, coefficient of variation 18%) 1.2 Gelatin 2.5 ExS-1 3 × 10 ^-4 ExS-2 1.5 × 10 ^-4 ExS-3 0.45 × 10 ^-4 ExC-4 0.15 ExC-5 0.05 ExC-2 0.03 ExC-3 0.01 Solv-1 0.05 Solv-2 0.3 Fifth layer (intermediate layer) Gelatin 0.8 Cpd-2 0.05 Solv-3 0.01 Sixth layer (low sensitivity green emulsion layer) Monodisperse silver iodobromide emulsion (5 mol% silver iodide) , Average particle size 0.3μ
m, coefficient of variation 19%) 0.4 monodisperse silver iodobromide emulsion (silver iodide 7 mol%, average grain size 0.5 μ)
m, coefficient of variation 20%) 0.8 Gelatin 3.0 ExS-4 1 × 10 ^-4 ExS-5 4 × 10 ^-4 ExS-6 1 × 10 ^-4 ExM-6 0.2 ExM-7 0.4 ExM-8 0.16 ExC-9 0.05 Solv-2 1.2 Solv-4 0.05 Solv-5 0.01 7th layer (high sensitivity green emulsion layer) Polydisperse silver iodobromide emulsion (3.5 mol% silver iodide, average grain size 0.8μ)
m, coefficient of variation 15%) 0.9 Gelatin 1.6 ExS-4 0.7 × 10 ^-4 ExS-5 2.8 × 10 ^-4 ExS-6 0.7 × 10 ^-4 ExM-7 0.05 ExM-8 0.04 ExC-9 0.01 Solv-1 0.08 Solv-2 0.3 Solv-4 0.03 8th layer (yellow filter layer) Yellow colloidal silver 0.2 Gelatin 0.9 Cpd-2 0.2 Solv-2 0.1 9th layer (low sensitivity blue emulsion layer) Monodisperse silver iodobromide emulsion (iodine Silver halide 6 mol%, average grain size 0.3μ
m, coefficient of variation 20%) 0.4 monodisperse silver iodobromide emulsion (5 mol% silver iodide, average grain size 0.6μ)
m, coefficient of variation 17%) 0.4 Gelatin 2.9 ExS-7 1 × 10 ^-4 ExS-8 1 × 10 ^-4 ExY-10 1.2 ExC-3 0.05 Solv-2 0.4 Solv-4 0.1 10th layer (high sensitivity blue feeling) Emulsion layer) Monodisperse silver iodobromide emulsion (6 mol% silver iodide, average grain size 1.5μ)
m, coefficient of variation 14%) 0.5 Gelatin 2.2 ExS-7 5 × 10 ^-5 ExS-8 5 × 10 ^-5 ExY-10 0.4 ExC-3 0.02 Solv-2 0.1 11th layer (1st protective layer) Gelatin 1.0 Cpd -3 0.1 Cpd-4 0.1 Cpd-5 0.1 Cpd-6 0.1 Solv-1 0.1 Solv-4 0.1 12th layer (2nd protective layer) Fine grain silver bromide emulsion (average grain size 0.07 μm) 0.25 Gelatin 1.0 Polymethylmethacrylate Particles (diameter 1.5 μm) 0.2 Cpd-8 0.5 In addition, a surfactant Cpd-7 and a hardener H-1 were added.

The color light-sensitive material produced as described above was processed by using an automatic processor in the same manner as in Example-1. According to the treatment using the bleaching solution of the present invention, Sample 401 of the present invention had a small post-treatment yellow stain and a small increase in color over time.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material containing at least one yellow coupler represented by the following general formula (I) is color-developed and then the bleaching solution is replenished with 100 to 1000 ml per 1 m ² of the light-sensitive material. In the treatment method, the bleaching solution contains 1,3-diaminopropanetetraacetic acid ferric iron complex salt in an amount of 0.2 mol / l or more, and 1 to 10 mol% of the ferric iron complex salt in 1,3-diaminopropanetetraacetic acid. Containing and pH 3-5
And a method for processing a silver halide color photographic light-sensitive material. General formula [I] (In the general formula [I], R ₁ is a tertiary alkyl group or an aryl group, R ₂ is a hydrogen atom, a halogen atom, an alkoxy group or an aryloxy group, and R ₃ is a halogen atom, an alkyl group, an aryl group or an alkoxy group. , An alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group,
A ureido group or an alkoxycarbonylamino group, X
Is a nitrogen atom and represents a heterocyclic group bonded to the coupling active position of the yellow dye-forming coupler represented by the general formula [I], and l represents an integer of 0 to 4, respectively. However, when 1 is plural, R ₃ may be the same or different. )