JPH0827523B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and in particular, finishing performance and image storability are obtained even if the processing time after color development is shortened. The present invention relates to an improved processing method that does not impair

(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 developing step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and thereafter, by a complexing agent of silver ions, commonly known as a fixing agent. Is dissolved. Through the desilvering process, only a 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.

Especially, the color negative film which is widely used requires a very long processing time as compared with a printing light-sensitive material such as a color paper, so that the request for shortening the processing time is becoming stronger.

At present, various color negative films have been released by many manufacturers, and it is an important requirement to properly finish each color negative film for processing.
Therefore, shortening the color development step that has the greatest effect on the finishing performance may impair the versatility of the processing, and shortening the processing step after color development has been desired.

Against this background, the bleaching process, fixing process, washing process,
Various studies have been conducted to reduce the time required for the stabilization process, etc.
The bleaching agent, fixing agent, stabilizer and the like have been shortened year by year by improving and agitating to enhance fixing and washing.

For example, in the CN-16Q processing carried out by the processor FP-350 for processing color negative film manufactured by Fuji Photo Film Co., Ltd., after the color development, until the end of the processing in the final bath,
It took about 15 minutes with the conventional standard processing, but it has been reduced to about 6 minutes and 30 seconds.

However, if the time after such color development is shortened to within 6 minutes, the problem that magenta stains increase during storage of the processed color negative film has become apparent.

Among the steps after color development, one of the steps that has conventionally required a long time is a bleaching step, and many methods have been proposed for shortening the bleaching step. Among them, the bleaching solution containing 1,3-diaminopropanetetraacetic acid ferric iron complex salt described in JP-A-62-222252 having a pH of about 6 has a strong oxidizing power and is currently widely used as ferric ethylenediaminetetraacetic acid. It enables more rapid silver bleaching compared to bleaching solutions mainly composed of complex salts. However, when this bleaching solution is used for direct bleaching without a bath in the middle after color development, there is a drawback that remarkable color fog called bleach fog is generated.

Therefore, even when such a rapid bleaching solution is used, it is impossible to reduce the time due to the problem of bleaching fog and the deterioration of the image storability due to the reduction in the time after the color development.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a rapid processing method in which the image storability is not deteriorated even if the time required to complete the processing in the final bath after color development is shortened to within 3 minutes. Another object is to provide a rapid processing method with excellent finishing performance that does not cause bleaching fog even when the bleaching time is shortened by using a bleaching solution having strong oxidizing power as a means for shortening the time. Is to provide.

(Means for Solving the Problems) An object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material within 3 minutes after color development until the processing in a final bath is completed. Diiron complex salt
It was achieved by a method of processing a silver halide color photographic light-sensitive material, which comprises processing with a bleaching solution containing 0.2 mol / l or more and having a pH of 3.0 or more and 5.0 or less.

That is, according to the method of the present invention, the deterioration of the image storability, which occurred when the processing time after the conventional color development was set within 6 minutes, was completely suppressed. Further, the problem of bleaching fog that occurs when using a bleaching solution containing a ferric complex of 1,3-diaminopropanetetraacetic acid disclosed in JP-A-62-222252 has been completely solved.

Although the mechanism of such effects of the present invention is unknown, the remarkable increase in the residual amount of the active ingredient in the processed photosensitive material, which is usually observed when the time after color development is shortened, tends to be suppressed in the present invention. According to the present invention, it is presumed that washing out of the color developing agent in the light-sensitive material is promoted and deterioration of image storability is prevented.

Also, the bleaching fog when using a bleaching solution of ferric complex of 1,3-diaminopropanetetraacetic acid is also set to a specific area on the more acidic side, which is out of the area around normal pH 6,
I was able to resolve it.

In the present invention, processing within 3 minutes until the end of processing in the final bath after color development means that one point of the light-sensitive material comes into contact with the liquid surface in the next step of color development, and It means that the time to escape from the liquid surface is within 3 minutes.

The effect of the present invention is extremely remarkable within 3 minutes.

 Hereinafter, the processing method of the present invention will be described.

In the present invention, desilvering is usually performed immediately after color development. Typical processing steps in the present invention are as follows.

Bleaching bath-Fixing bath Bleaching bath-Bleaching fixing bath Bleaching bath-Washing bath-Fixing bath Here, the bleaching bath and fixing bath may be one tank or two or more tanks (for example, 2 to 4 tanks, in this case, countercurrent method). Is preferred).

In the method of the present invention, a step is particularly preferred. The steps are described in, for example, JP-A-61-75352.

A ferric complex of 1,3-diaminopropanetetraacetic acid is used in the bleaching solution of the present invention.
It is 2 mol or more, preferably 0.25 mol or less, and particularly preferably 0.3 mol or more for speeding up. However, excessive use conversely inhibits the bleaching reaction, and the upper limit is 0.5 mol. The ferric complex salt of 1,3-diaminopropanetetraacetic acid can be used as a salt of ammonium, sodium, potassium, or the like, but an ammonium salt is preferred because bleaching is the fastest.
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. Further, the pH of a bleaching solution containing a ferric aminopolycarboxylic acid complex is conventionally adjusted to pH 6 from the standpoints of securing a bleaching rate and preventing the color recovery failure of a cyan dye.
The neighborhood has been optimized and has been widely practiced. That is, low pH
Although the bleaching speed was improved by this conversion, the optimum balance was considered to be around pH 6 because the cyan dye causes defective recoloring.

On the other hand, the present invention has the characteristic that the effect is exhibited by setting the pH of the bleaching solution to 5.0 or less, and is contrary to the conventional trade-off that a rapid desilvering and complete restoration of the cyan dye can be achieved. Solve the problem The bleaching solution of the present invention
pH is 5.0-3.0, the preferred region of effect expression is 4.5
~ 3.5. To adjust the pH to this range, organic acids such as citric acid acetate, malonic acid, etc. and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid can be used, but the acid dissociation index (PKa) is 2.5.
Acid in the range of to 5.5 has a buffer property in the region of the present invention, and is preferable in enhancing the effect of the present invention, in addition to the acetic acid, citric acid, malonic acid, benzoic acid, formic acid, butyric acid, malic acid, Various organic acids such as tartaric acid, oxalic acid, propionic acid and phthalic acid can be mentioned. Among these, acetic acid, tartaric acid and citric acid are particularly preferable.

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 that 1,3-diaminopropanetetraacetic acid is added to the bleaching solution in a slightly excessive amount, which is necessary for complex formation with ferric ion, and usually in an amount of 1 to 10%. preferable.

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. Pat.No. 3,893,858, German Patent 1,290,812, British Patent 1,138,842, JP-A-53-95630, Research Disclosure No. 17129 (1978
A compound having a mercapto group or a disulfide group described in July, July, 1991, a thiazolidine derivative described in JP-A-50-140129, a thiourea derivative described in U.S. Pat. The iodides described in 16235, the polyethylene oxides described in German Patent No. 2,748,430, the polyamine compounds described in JP-B-45-8836, and the like 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 replenishment amount of the bleaching solution of the present invention is 50 ml to ² per m2 of the light-sensitive material.
It is 000 ml, preferably 100 ml to 1000 ml.

During the treatment, it is preferable that the bleaching solution is subjected to aeration to oxidize the produced 1,3-diaminopropanetetraacetic acid ferrous complex salt.

 The light-sensitive material after bleaching is then usually subjected to fixing processing.

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, it is preferable to use ammonium thiosulfate, and the amount thereof is 0.3 to 3 mol per 1 fixer, preferably
0.5 to 2 mol.

From the viewpoint of accelerating fixing, it is also preferable to use the above-mentioned ammonium thiocyanate (ammonium rhodanate), thiourea and thioether (for example, 3,6-dithia-1,8-octanediol) in combination, and the amount of these compounds used in combination. Is
The amount is generally 0.01 mol to 0.1 mol per 1 fixing solution, but if necessary, 1 to 3 mol can be used to greatly enhance the fixing promoting effect. An example of such a fixer is Research Disclosure 22110 (1982.9).
Those described in are preferable.

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. . Furthermore, various fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol can be contained, and particularly as preservatives are described in Japanese Patent Application No. 60-283831. It is preferable to use a 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 (bleaching process and fixing process) of the present invention, the more remarkable the effect of the present invention is obtained. The preferred time is 1 minute to 4 minutes, more preferably 1 minute 30 seconds to 3 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
Is. In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented.

In the present invention, the fixing treatment is followed by a washing or stabilizing treatment or a washing treatment followed by a stabilizing treatment.

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 LE
West, “Water Quality Criteria”, Phot.Sci.and Eng., V
The compounds described in ol. 9, No6, 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 stabilizing steps is not limited to tap water, but may be 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 light-sensitive material, when the continuous processing by the automatic developing machine is performed, the processing solution may be concentrated by evaporation, especially when the processing amount is small or the opening area of the processing solution is large. It becomes remarkable. 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 washing or stabilizing time is preferably 20 seconds to 2 minutes, and particularly preferably 30 seconds to 1 minute 30 seconds. The stabilization treatment after washing with water is preferably 5 seconds to 1 minute, and particularly preferably 10 seconds to 40 seconds.

In the step after color development of the present invention, it is preferable that stirring is strengthened as much as possible so that the effects of the present invention can be more effectively exhibited.

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 a photosensitive material, a method of increasing the stirring effect by using a rotating means of Japanese Patent Application Laid-Open No. 62-183461, A method of improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade to make the emulsion surface turbulent, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of a bleaching solution, a bleach-fixing solution and a 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, as a result, the despeeding rate.

Further, the agitation improving means is more effective when a bleaching accelerator is used, and can significantly increase the accelerating result or eliminate the fixing inhibition effect by 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 JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and has a high effect of preventing the performance fixed value of the treatment liquid. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The effect of the present invention is remarkable when the processing time after color development is short, specifically, it is clearly demonstrated when the processing time is 5 minutes or less, and when 3 minutes or less, the difference from the conventional processing method is more remarkable. Becomes Therefore, in the present invention, the processing time after color development is preferably 5 minutes or less, and particularly preferably 3 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 typical 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-
(Methanesulfonamide) 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 Of 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 developing solution is preferably 0.1 mol / l or more, and particularly 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- Diphosphonic 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
-5987, 38-7826, 44-12380, 45-9019 and U.S. Pat.No.3,813,247, thioether compounds represented by JP-A-52-49829 and JP-A-50-15554. P-phenylenediamine compound, 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, etc. 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, imidazole, 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 alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added.

The processing temperature of the color developer of the present invention is from 20 to 50 ° C, preferably from 30 to 40 ° C. Processing time is 20 seconds to 5 minutes, preferably 30
Seconds to 2 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 a developing agent such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, a preservative such as sulfite, and an accelerator composed of an alkali such as sodium hydroxide, sodium carbonate or 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 light-sensitive material processed by the method of the present invention may have at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer of a silver halide emulsion layer provided on a support. There is no limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red color-sensitive layer and the green color. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed according to 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 various intermediate layers 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 / BL /
They can be installed in the order of 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-59-2
As described in the specification of No. 02464, middle-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 that can be used in the present invention is described, for example, in Research Disclosure (RD) No. 17643 (1978).
December), pp.22-23, "I. Emulsion preparatio
n and types) ”, and No. 18716 (November 1979), 64
8 pages, Physique and Physics of Chemistry, published by Paul Montel (P.Glafkides, Chemic et Phisique Photograp
hique, Paul Montel, 1967), Duffin's "Photoemulsion Chemistry", published by Focal Press (GFDuffin, Photographi).
c Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., 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), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,433,048, 4,439,520
It can be easily prepared by the method described in Japanese Patent No. 2,112,157 and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and the silver halide having a different composition may be bonded by epitaxial bonding. Or 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. Additives used in such processes are 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, US 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 are described in the patents described in the above-mentioned Research Disclosure (RD) No. 17643, VII-C-G.

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, 4,511,649, European Patent 249,473A, and the like are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. No. 4,310,61
No. 9, No. 4,351,897, European Patent No. 73,636, U.S. Pat. No. 3,061,432, No. 3,725,064, Research Disclosure No. 2422 (June 1984), JP-A-60-33552.
No., 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.

Cyan couplers include phenol and naphthol couplers, 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 are also preferably used in the present invention. DIR couplers that release development inhibitors are RD17643, VII-F described 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 processed by the method of the present invention include U.S. Pat. No. 4,130,427.
Competitive couplers described in U.S. Patent No. 4,283,472,
No. 4,338,393, No. 4,310,618, etc., multi-equivalent couplers, JP 60-185950, JP 62-24252, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing Redox compound or DIR redox releasing redox compound, European Patent No. 17
Couplers releasing a dye that undergoes color recovery after separation described in 3,302A, RD No. 11449, 24241, bleaching accelerator releasing couplers described in JP-A No. 61-201247, U.S. Pat. Ligand releasing coupler, JP-A-63-75747
And the couplers that release the leuco dye described in No.

The coupler used in the light-sensitive material processed in the present invention is
It can be incorporated 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 high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate and the like, esters of phosphoric acid or phosphonic acid ( Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, dichloropropyl phosphate 2
-Ethylhexylphenyl phosphate, etc.), Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecane amide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Amylphenol, 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-tert
Octylaniline), 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 of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US 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 light-sensitive material processed according to the present invention include, for example, RD.No. 17643, page 28, and the same No.
18716, page 647, right column to page 648, left column.

The total thickness of all hydrophilic colloid layers on the emulsion layer side of the light-sensitive material processed by the method of the present invention is preferably 8 μm or less and the film swelling speed T1 / 2 is preferably 30 seconds or less. The film thickness is
The film swelling rate T1 / 2 means the film thickness measured under the condition of 25 ° C. and 55% relative humidity (2 days), and can be measured according to a method known in the art. For example, A. Green et al., Photographic Science and Engineering (Pho.Sci.Eng.), Volume 19,
No. 2, pages 124-129, swellometer (swelling meter)
Can be measured by using the
90% of the maximum swollen film thickness reached when treated at 3 ℃ for 15 minutes
Is defined as the saturated film thickness, and is defined as the time required to reach this T1 / 2 film thickness.

The film swelling speed T1 / 2 can be adjusted by adding a 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 conditions described above according to the following formula (maximum swelling film thickness-film thickness) / film thickness.

(Examples) Hereinafter, the present invention will be specifically described with reference to Examples.

Example 1 Sample 101, 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.

1st layer (anti-halation 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 Second Layer (intermediate layer) Fine grain 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, spherical equivalent diameter 0.
3 μm, coefficient of variation of equivalent sphere 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 ^-5 ExS-2 …… 3.0 × 10 ^-4 ExS-3 …… 1 × 10 ^-4 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 (2nd red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 5 mol%, internal high AgI type, spherical equivalent diameter 0.
7 μm, variation coefficient of equivalent spherical diameter 25%, normal crystal, twin crystal 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-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, spherical equivalent diameter)
0.8 μm, variation coefficient of equivalent spherical 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) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, equivalent spherical diameter 0.
3 [mu] m, a variation coefficient of 28% equivalent spherical diameter, normal crystal, twin crystal mixed grains, 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, spherical equivalent diameter 0.
6 μm, coefficient of variation 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 (No. 3 Green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type, equivalent spherical 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 Eleventh layer (first blue emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal) High AgI type, sphere equivalent diameter 0.
5 μm, variation coefficient of equivalent spherical diameter of 15%, octahedral particles) 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 emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent spherical diameter)
1.3 μm, coefficient of variation of equivalent sphere 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 2 Protective layer) Fine 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 is subjected to running processing by using an automatic processor and the following processing steps and processing solutions.

In Table 1, the time from color development to the end of stabilization is 3 minutes and 15 seconds.

(Stabilizer) Mother liquor, 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 A specific method for running 1.0 l pH 5.0-7.0 with water is as follows.

The light-sensitive material was cut into a width of 35 mm, standard exposure was given in the camera, and this was processed for 500 m to bring each solution into a steady running state. Next, ammonia water and acetic acid were added to the bleaching solution to adjust the pH shown in Table-2.

Also, when the light-sensitive material after color development enters the bleaching solution,
The effect of the present invention was evaluated by changing the conveying speed of the automatic processor and changing the time from color development to the end of the stabilizing solution as shown in Table-2.

Here, the time of each step after color development in Table 1 is
The ratio varies between the “processing time after color development” shown in Table 2 and the time of 3 minutes and 15 seconds shown in Table 1.

Under the above conditions, the photosensitive material has a color temperature of 4800K, 20C.
It was processed by applying a wet exposure of MS, and the amount of residual silver in the maximum density part (measured by the fluorescence X-ray method) and No. 5 in Table-2 were used as the standard, and the transmission yellow density (exx light The difference was measured with a Model 310 photograph densitometer).

Further, the same sample was stored for 1 week under the conditions of 60 ° C. and a relative humidity of 70%, and the change in magenta concentration (change in magenta stain) in the lowest concentration part was measured.

 The above results are shown in Table 2.

As shown in Table-2, when the bleaching solution has a pH of 6 (No.1)
Has a very high yellow density in the lowest density area, causing remarkable bleaching fog. It is also found that when the processing time after color development is shortened (No. 2), the magenta stain after storage under high temperature and high humidity increases remarkably.

On the other hand, according to the present invention in which the pH is 5.0 or less, the above problems are remarkably improved, and it is clear that the range of pH 3.5 to 4.5 is extremely preferable. However, if the pH is lowered below 3.0, the desilvering property deteriorates, and it is considered to be an acceptable level of 5 μg / cm ²
The result is that the residual silver amount of is greatly exceeded.

Example 2 Sample 101, 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 1st layer (Anti-halation 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, equivalent spherical diameter 0.4)
[mu] m, spherical coefficient of variation of 37% equivalent diameter, the plate-like particles, diameter / thickness ratio 3.0) coating silver 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 inside) High
AgI type, sphere equivalent diameter 0.65μm, sphere equivalent diameter variation coefficient 25%,
Tabular grains, diameter / thickness ratio 2.0) coated silver amount 0.65 silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter 0.4)
[mu] m, spherical coefficient of variation of 37% equivalent diameter, the plate-like particles, diameter / thickness ratio 3.0) coating silver 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 inside) High
AgI type, sphere equivalent diameter 0.7 μm, coefficient of variation of sphere equivalent diameter 25%, plate-like particles, diameter / thickness ratio 2.5) coated silver 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 Layer 6 (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter) 0.4
[mu] m, spherical coefficient of variation of 37% equivalent diameter, the plate-like particles, diameter / thickness ratio 2.0) coating silver 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 (medium sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, surface with core shell ratio 1: 1) High
AgI type, equivalent sphere diameter 0.5 μm, variation coefficient of equivalent sphere diameter 20%, plate-like 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%, Multilayer structured particles with a silver amount ratio of 3: 4: 2, AgI content from the inside of 24 mol, 0 mol, 3 mol%, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 25%, plate-like particles, diameter / Thickness ratio 1.6) Silver coating 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 (Donator layer having a multi-layer effect on the red-sensitive layer) Silver iodobromide emulsion (AgI 6 mol%, core shell ratio 2: 1
AgI type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grain, diameter / thickness ratio 2.0) Coating silver amount 0.68 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter) 0.4
μm, variation coefficient of equivalent sphere diameter 37%, plate-like particles, diameter / thickness ratio 3.0) Coating silver 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, spherical equivalent diameter 0.
7 μm, coefficient of variation of sphere equivalent diameter 15%, tabular grain, diameter / thickness ratio 7.0) coated silver amount 0.3 silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μm, coefficient of variation of equivalent sphere diameter 30%, plate-like particles, diameter / thickness ratio 7.0) coated silver 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 Layer 13 (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, variation coefficient of equivalent spherical diameter 25%, multiple twin plate 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) Coating silver 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 (2nd protective layer) Fine grain silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, equivalent spherical diameter 0.07 μm) coated Silver amount 0.36 Gelatin 0.55 Polymethylmethacrylate particles (diameter 1.5 μm) 0.2 H-1 0.17 In addition to the above components in each layer, emulsion stabilizer Cpd-3
(0.03 g / m ² ) and the 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 used in Example-1.
In the same manner as in (1), the following processing steps and processing solutions were used using an automatic processor.

In Table 3, the time required for stabilization after color development is 3
Minutes.

(Washing 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 sodium isocyanurate dichloride 20 mg / l and sodium sulfate 0.15 g / l were added.

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

The running method is the same as in Example-1.

After the running was completed, ferric complex of 1,3-diaminopropanetetraacetic acid was added to the bleaching solution to obtain the concentrations shown in Table 4, and the pH of the bleaching solution was variously changed by using acetic acid and ammonia.

Then, the photosensitive material was subjected to a wet exposure of 4800 K and 20 CMS, the same items as in Example-1 were evaluated by the same method, and the results are shown in Table-4. The difference in yellow density is shown based on Table 4 No. 5.

As is clear from Table 4, the concentration of the ferric complex of 1,3-diaminopropanetetraacetic acid was less than 0.2 mol / l (N
In o.1), the residual silver amount greatly exceeded the allowable level, and
The change (increase) in magenta stain is also remarkable. Also, the bleaching fog seen in the yellow density is relatively large.

On the other hand, according to the present invention, the above-mentioned problems are remarkably ameliorated, in particular, the concentration of 1,3-diaminopropanetetraacetic acid ferric iron complex is 0.25 mol / l to 0.4 mol / l, and the pH is 3 to 5. It is clear that the range is particularly preferred.

Example 3 On the undercoated cellulose triacetate film support, each layer having the composition shown below was coated in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive 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 (anti-halation layer) Black colloidal silver 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 4th layer (2nd red 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 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) Milk Agent 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 Eighth layer (2nd 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 (first 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 (2nd blue-sensitive emulsion layer) Emulsion G Silver 0.45 Sensitizing dye VIII 2.1 × 1 0 ^-4 EX-9 0.154 EX-10 0.007 HBS-1 0.05 Gelatin 0.78 13th layer (3rd blue 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, gelatin hardener H-1 and a surfactant were added to each layer.

HBS-1 Tricresyl Phosphate HBS-2 Di-n-butylphthalate The above light-sensitive material was exposed in the same manner as in Example-1 and processed in the same manner as in Example-1.

Then, the photosensitive material was subjected to a wet exposure of 4800 K and 5 CMS, and the difference between the residual silver amount and the yellow density (No. 1 standard) was determined in the same manner as in Example-1, and the relative humidity at 60 ° C was also used.
The change in cyan density (cyan stain) in the lowest density part when stored at 70% for 2 weeks was determined.

Next, 1,3-diaminopropanetetraacetic acid ferric iron complex salt and 1,3-diaminopropanetetraacetic acid complex of the bleaching solution of Example-1 were treated with ethylenediaminetetraacetic acid ferric iron complex salt and its free acid, diethylenetriaminepentaacetic acid and its The acid was changed to the free acid and evaluated in the same manner as above.

 The above results are shown in Table-5.

The difference in yellow density is shown based on Table 5, No. 1.

The bleaching solutions of Nos. 1 to 3 in Table 5 were adjusted to pH 4.3.

As shown in Table 5, it is understood that the effect of the present invention is specifically obtained by the ferric complex of 1,3-diaminopropanetetraacetic acid.

Example-4 In Example-2, all overflow of the bleaching solution accompanying replenishment was made to flow into the fixing, and the same procedure as in Example-2 was carried out. As a result, the residual silver amount was further reduced as compared with the results in Table-4. However, it was confirmed that a better desilvering performance was obtained.

Claims (1)

[Claims] 1. A method in which a silver halide color photographic light-sensitive material is processed within 3 minutes after color development in a final bath until completion of processing, and 0.2 mol / l or more of 1,3-diaminopropanetetraacetic acid ferric iron complex salt is used. A method of processing a silver halide color photographic light-sensitive material, which comprises processing with a bleaching solution having a pH of 3.0 to 5.0.