JPH02282740A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce bleaching fog (color fog) and the occurrence of stains at a part developing no color during the storage of an image after processing by adding a specified amt. of an oxidizing agent having a specified oxidation- reduction potential or above and an acid having specified pKa to a bleaching bath. CONSTITUTION:An oxidizing agent having >=150mV oxidation-reduction potential and an acid having 2-5 pKa are added to a bleaching bath by >=1.2mol/l. The pKa is the cologarithm of the dissociation constant of the acid measured at 0.1mol/l ionic strength and 25 deg.C. Bleaching fog and the occurrence of stains during storage can be reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically, a method for rapidly bleaching silver halide color photographic materials using an improved bleaching solution in the desilvering process. This invention relates to a processing method that produces less bleaching capri and less staining when images are stored after processing.

(Prior Art) In general, the basic steps of processing silver halide color photographic materials (hereinafter referred to as color photographic materials) are a color development step and a desilvering step, in which halogens are exposed to light by a color developing agent. In the zero-order desilvering process, in which silver oxide is reduced to produce silver, and the oxidized color developing agent reacts with a color former (coupler) to form a dye image, the action of an oxidizing agent commonly called a bleaching agent is used. As a result, silver produced in the color development process is oxidized and then dissolved by a silver ion complex ion forming agent commonly called a fixing agent. By going through this desilvering step, only a dye image is created on the color photosensitive material.

The above desilvering process is carried out in two baths, a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, a method in which a bleach-fixing bath containing both a bleaching agent and a fixing agent is carried out in one bath, and a method in which a bleaching bath and a fixing bath are carried out in one bath. There is a method of carrying out the process using two baths: a bath and a bleach-fixing bath, and each bath may be carried out in multiple baths.

In addition to the basic steps mentioned above, the actual development process includes various auxiliary steps to maintain the photographic and physical quality of the image, or to improve the preservation of the image. bath, stop bath, image stabilization bath, washing bath, etc.

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

In particular, the highest demand was to shorten the desilvering step, which conventionally occupied most of the processing time.

However, the ferric complex salt of ethylenediaminetetraacetic acid, which is the main bleaching agent used in bleaching solutions and bleach-fixing solutions, has the basic drawback of weak oxidizing power, so it is often used in combination with bleaching accelerators, etc. Despite the improvements that have been made, the above requirements have not yet been met.

On the other hand, as bleaching agents with strong oxidizing power, red blood salt, dichromate, ferric chloride, persulfate, bromate, etc. are known. The reality is that each method has a number of drawbacks, and cannot be widely used for over-the-counter processing.

Among these, for example, p containing a ferric complex salt of 1,3-diaminopropanetetraacetic acid having a high oxidizing power with a redox potential of 150 mV or more is described in JP-A No. 62-222252.
A bleaching solution with H of about 6 enables faster bleaching than a bleaching solution containing a ferric complex salt of ethylenediaminetetraacetic acid, but
If bleaching is performed directly after color development without using an intermediate bath, it has the disadvantage of generating color capri, which is called bleaching edge blur.

Furthermore, apart from this problem of bleaching edge blur, when processing with a shortened bleaching time using such a bleaching solution, a new problem arises: a large increase in staining occurs during storage of color photosensitive materials after processing. It became clear what was going to happen.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a processing method that reduces bleaching blade blur (color fog) and staining in uncolored areas that occurs when storing images after processing. A second object of the present invention is to provide a rapid processing method that achieves the first object and also has excellent desilvering properties.

(Means for Solving the Problems) The present inventors have discovered that the above problems can be achieved by the method described below.

That is, after imagewise exposure of a silver halide color photographic material,
In a processing method in which a color developing treatment is performed with a color developing solution containing an aromatic primary amine color developing agent, and then a bleaching treatment is performed with a bleaching solution, the bleaching solution has an oxidation-reduction potential of 150m.
1.2 mol/of an oxidizing agent of V or more and an acid of pKa 2 to 5
This could be achieved by a treatment method characterized by containing I1 or more.

The present invention will be described in detail below.

Typical desilvering treatment steps in the present invention are as follows.

■Bleach bath - constant wearing ■Bleach bath - bleach-fixing bath ■Bleach bath - washing bath - constant wearing ■Rinse bleach bath - constant wearing ■Bleach bath - bleach-fixing bath - constant wearing ■Washing - bleach-fixing bath Here, bleach bath Even if there is only one fixing bath, two or more (
For example, it may be 2 to 4 tanks (in which case a countercurrent system is preferred).

In the present invention, remarkable effects are achieved when desilvering treatment is performed immediately after color development.

Particularly preferred are steps (1), (2), and (2). Step (2) is disclosed in, for example, Japanese Patent Application Laid-open No. 75352/1983.

The oxidation-reduction potential of the oxidizing agent (bleaching agent) in the bleach solution described in this invention is based on the Transactions of the Faraday.
Society (Transactions of
e Foraday 5ociety), Volume 55 (
It is defined by the oxidation-reduction potential measured by a method described in 1959), pp. 1312-1313.

The bleaching solution of the present invention uses an oxidizing agent having a redox potential of 150 mV or more under the condition of pl (=6.0) obtained by the method described above.

Oxidizing agents with a redox potential of 150 mV or more at pH = 6.0 include inorganic compounds such as red blood salt, ferric chloride, dichromate, persulfate, and bromate, and iron aminopolycarboxylate (II).
I) Some of the complex salts include organic compounds. In the present invention, aminopolycarboxylic acid iron (III) i! Preference is given to using salt.

Aminopolycarboxylic acid iron (III) t! Some specific examples of salt compounds include: 1. Iron N-(2-acetamido)iminodiacetate (I
II) Complex Z iron methyliminodiacetate (![)i! Salt 3, Iron iminodiacetate (I
l) Complex salt 6, iron glycol ether diamine tetraacetate (Ill)
complex salt? , 1,3-propylenediaminetetraacetic acid iron ([[[)if salt 25-0, etc.]. Among these compounds, particularly preferred is 1.3-propylenediaminetetraacetic acid iron ([1) complex salt (hereinafter referred to as 1.3DPTA-Fe (Il
(abbreviated as l)).

In addition, ethylenediaminetetraacetic acid iron (m) complex salt (EFTA-Fe (Ill)), which is widely used in the industry, is 1
) 0 mV, diethylenetriamine five-node M iron (Il
l) 1M salt, trans-1,2-cyclohexanediaminetetraacetic acid iron (Ill) fit salt, etc. have a voltage of 80 mV, and are excluded from the oxidizing agents of the present invention.

The preferred redox potential of the present invention is 180 mV or more. More preferably, it is 200 mV or more.

The amount of oxidizing agent used in the bleaching solution of the present invention is preferably 0.10 mol or more per 1 liter of bleaching solution, and more preferably 0.15 mol or more in terms of speeding up the processing and reducing bleach fog and stain. Particularly preferred is 0.25 mol or more.

However, the upper limit of the concentration is 0.7 mol because the use of an excessively high concentration solution will actually inhibit the bleaching reaction. PH=6.0
Aminopolycarboxylic acid iron ([I) with a redox potential of 150 mV or more is used as a salt such as sodium, potassium, ammonium, etc., but ammonium salt is preferable because it bleaches the fastest. In addition, if the concentration of the aminopolycarboxylic acid iron (I[I) complex salt is less than 0.10 mol/l, bleaching will be rapidly delayed. Therefore, the present invention provides 0.1
Preferably, the concentration is 0 mol/l or more.

In addition, these aminopolycarboxylic acid iron (m) complex salts have 2
It is also possible to use a mixture of more than one species.

In addition, in the present invention, the redox potential is set to pH=6゜0.
As shown in the potential determined in , when the color photosensitive material enters the bleach solution after the color development process is completed, the pH in the film of the color photosensitive material decreases. This pH
If the pH decreases quickly, the bleach fog will be small, but if the pH decreases slowly or if the pH of the bleaching solution is high, the bleach fog will be high.From these facts, p [(6) is the standard for bleach fog to occur. Therefore, pH=
6.0 was taken as the pH for comparing redox potentials.

Next, pKa2 to 5 used to achieve the object of the present invention
Explain about the acid.

In the present invention, pKa represents the logarithm of the reciprocal of the acid dissociation constant, and has an ionic strength of 0.1 mol/l. The values determined at 25°C are shown.

The present invention is characterized in that a bleaching solution containing 1.2 mol or more of an acid having a pKa in the range of 2.0 to 5.0 is used in the desilvering step. pKa2.0-5 for bleaching solution
．． It has surprisingly been found that by containing 1.2 mol/l or more of 0 acid, bleaching edge blur, increased staining in uncolored areas after processing, and desilvering properties can be improved.

This pKa2. The acid with Q~5.0 may be any inorganic acid such as phosphoric acid, or organic acid such as acetic acid, malonic acid, citric acid, etc.;
Acids between 2.0 and 5.0 are organic acids. Among organic acids, organic acids having a carboxyl group are particularly preferred.

An organic acid with a pKa of 2.0 to 5.0 may be a monobasic acid or a polybasic acid. If it is within this range, it can be used as a metal salt (for example, sodium or potassium salt) or ammonium salt. In addition, organic acids with pKa of 2.0 to 5.0 are
It is also possible to use a mixture of more than one species. However, aminopolycarboxylic acids and their Fe complex salts are excluded.

Preferred specific examples of organic acids with a pKa of 2.0 to 5.0 used in the present invention include formic acid, acetic acid, monochloroacetic acid,
Monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, glycolic acid, acrylic acid,
Aliphatic-basic acids such as acetic acid, isomeric acid, hyalic acid, aminobutyric acid, valeric acid, isovaleric acid; asparagine, alanine, arginine, ethionine, glycine, glutamine,
Amino acid compounds such as cysteine, serine, methionine, and leucine; Aromatic-basic acids such as benzoic acid and monosubstituted benzoic acids such as chloro and hydroxy, and nicotinic acid;
Aliphatic tribasic acids such as oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid, adipic acid; aspartic acid, glutamic acid, glucuric acid, cystine, ascorbic acid Various organic acids can be listed, such as amino acid-based tribasic acids such as; aromatic dibasic acids such as phthalic acid and terephthalic acid; and polybasic acids such as citric acid.

In the present invention, among these, monobasic acids having a carboxyl group are preferred, and acetic acid is most preferably used.Furthermore, the organic acids of the present invention do not include aminopolycarboxylic acid ferric complex salts, which are bleaching agents.

In the present invention, the amount of these acids used is 1.2 mol or more per bleaching solution 1). Preferably 1.2 to 2.5
Mol/l. More preferably 1.5 to 2.0 mol/
It is.

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

A pH 6 bleaching solution containing 1,3-DPTA-Fe (III) is described in the above-mentioned JP-A-62-222252. Conventionally, the optimum pH of a bleaching solution containing an aminopolycarboxylic acid iron(1) complex salt has been set at around pH 6 from the viewpoint of both ensuring a high bleaching speed and preventing poor restoration of cyan dye, and this has been widely practiced. That is, although lowering the pH improves the bleaching rate, it causes poor recoloring of the cyan dye, so the optimum balance has been set around pH 6.

In contrast, in the present invention, the bleaching solution has p.

A value of 5.0 or less is preferable because the effect is effectively expressed.

In other words, it solves the problems that were considered to be contradictory in the past: rapid desilvering and complete restoration of cyan dye.
9H of the bleaching solution of the present invention is preferably 5.0 to 2°0, more preferably 4.5 to 2°5, most preferably 4.
．． It is 0 to 3.0. To adjust the pH to this range,
Known acids can be used. It may be the acid mentioned above.

When using a ferric aminopolycarboxylic acid complex salt in a bleaching solution, the aminopolycarboxylic acid may be added in slightly excess amount compared to the amount required to form a complex with ferric ions, and when added in excess, It is preferable to use an excess in the range of 0.01 to 10%.

Moreover, in the bleaching solution of the present invention, the redox potential is 150 mV.
When using the above iron aminopolycarboxylic acid (nntst salt), other ferric aminopolycarboxylic acid salts may also be used together, and the redox potential may be 150 mV or less. Specifically, Examples include ferric complex salts of enalediaminetetraacetic acid, diethylenetriamine5I% acid, and cyclohexanediaminetetraacetic acid.

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

Such bleach accelerators are described, for example, in U.S. Patent No. 3,893,858, German Patent No. 1,290
, 812 specification, British Patent Co., Ltd. 1) 38.842 specification, JP-A-53-95630, Research Disclosure No. 17129 (July 1978 issue) having a mercapto group or disulfide group Compounds, thiazolidine derivatives described in JP-A No. 50-140129, thiourea derivatives described in U.S. Pat. No. 3,706,561, iodides described in JP-A-58-16235, German patents Polyethylene oxides described in specification No. 2.748.430, Japanese Patent Publication No. 45-8
Polyamine compounds described in Japanese Patent No. 836 can be used. Particularly preferably British patent cylinder 1.138,8
Mercapto compounds such as those described in No. 42 are preferred.

In addition to the bleaching agent and the above-mentioned compounds, the bleaching solution constituting the present invention includes bromides such as potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide or chlorides such as potassium chloride, sodium chloride, ammonium chloride can be included.

The concentration of the rehalogenating agent is between 0.1 and 5 mol, preferably between 0.5 and 3 mol, per bleach solution 1).

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

The amount of replenishment of the bleaching solution of the present invention is 200 m per pot of photosensitive material.
j! Below, preferably 140mj! -IQml.

Further, the bleaching treatment time is 120 seconds or less, preferably 60 seconds or less, and more preferably 40 seconds or less.

In addition, during processing, it is preferable to aerate the bleaching solution using the aminopolycarboxylic acid iron (Ill) complex salt to oxidize the produced aminopolycarboxylic acid iron (n) iff salt. is subsequently bleach-fixed or fixed. The fixing treatment may be performed using a fixing solution or a bleach-fixing solution.

As the fixing agent, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate, potassium thousocyanate, thiourea, thioether, etc. are used. be able to. Among them, it is preferable to use ammonium thiosulfate.

The amount of fixer is from 0.3 to 3 mol, preferably from 0.5 to 2 mol, per fixer solution 1).

In addition, from the viewpoint of promoting fixation, the above-mentioned ammonium thiocyanate (rhodan ammonium), 1,000 urea, thioether (
For example, it is also preferable to use 3,6-cythia-1,8-octanediol) in combination, and the amount of these compounds used in combination is from 0.01 mol to 0.1 mol per liter of fixer or bleach-fixer.
The amount is generally about 1 mol, but in some cases, the fixing promotion effect can be greatly enhanced by using 1 to 3 mol.

The fixer or bleach-fixer contains sulfite as a preservative,
For example, sodium sulfite, potassium sulfite, ammonium sulfite, and hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, such as acetaldehyde sodium bisulfite, can be included. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained, but in particular, as preservatives,
It is preferable to use the sulfinic acid compounds described in Japanese Patent No. 0-283831.

The bleach-fix solution may contain the above-mentioned known bleaching agent, preferably an aminopolycarboxylic acid ferric complex salt.

In the bleach-fix solution, the amount of bleach per bleach-fix solution 1) is 0.01 mol to 0.5 mol, preferably 0.02 mol.
Mol~0. 3 mol, particularly preferably 0.03 to
It is 0.2 mole.

In the present invention, the bleach-fix solution (mother liquor) at the start of processing is
The bleach-fixing solution described above is prepared by dissolving the compound used in the bleach-fixing solution in water, but it may also be prepared by mixing appropriate amounts of separately prepared bleaching solution and fixing solution. The pH of the fixer is 5 to 9.
is preferable, and 7 to 8 are more preferable. In addition, the pH of the bleach-fix solution is preferably 6 to 8.5, more preferably 6 to 8.5.
．． 5-8°0 is preferable.

The replenishment amount of the fixing solution and bleach-fixing solution is 1rd for the photosensitive material.
It is preferably 300ml to 3000ml, more preferably 300nl! to 10100O.

Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixer and bleach-fixer for the purpose of stabilizing the solution.

The shorter the total processing time of the desilvering step of the present invention, the more remarkable the effects of the present invention can be obtained. The preferred time is 1 minute to 4 minutes,
More preferably, the time is 1 minute 30 seconds to 3 minutes. Further, the treatment temperature is 25'' to 50°C, preferably 35°C to 45°C.

In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step of the present invention, it is preferable that the stirring be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening stirring is disclosed in Japanese Patent Application Laid-Open No. 62-18346.
No. 0, No. 62-183461, the method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, and the method of colliding a jet of a processing liquid on the emulsion surface of a photosensitive material, as described in JP-A No. 62-183-1.
No. 83461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the light-sensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. method, and a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. Improving agitation is achieved by adding bleach into the emulsion film,
It is believed that this speeds up the supply of fixing agent and, as a result, increases the desilvering rate.

Further, the agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the bleach accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used in the present invention is disclosed in Japanese Patent Application Laid-Open No. 601912.
57, No. 191258, and No. 191259. As described in JP-A-60-191257, such a conveying means is used to transport the photosensitive material from the front bath to the post bath. It is possible to significantly reduce the amount of processing liquid brought into the system, and it is highly effective in preventing deterioration in the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The effect of the present invention is remarkable when the total development processing time is short, and specifically, it is clearly exhibited when the total development processing time is 8 minutes or less, and when it is 7 minutes or less, it is even more effective than the conventional processing method. The difference becomes noticeable. Therefore, in the present invention, the total treatment time is preferably 8 minutes or less, particularly 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,
Representative examples are shown below, but the invention is not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-5°2-methyl-4-[N-ethyl-N-Cβ-hydroxyethyl)aminocoaniline D-64-minnow 3-methyl-N-ethyl-N- (β
-(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl- N-ethyl N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-1) 4-amino-3-methyl-N-ethyl N-β-
Butoxyethylaniline Among the above p-phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferred.

Moreover, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. The amount of the aromatic primary amine color developing agent used is preferably about 0.1 g per liter of color developing solution.
to about 20 g, more preferably about 0.5 g to about log.

In addition, the color developer contains sodium sulfite and preservatives.
Sulfites such as potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts can be added as necessary.

The preferable amount of preservative added is 0.5 o per color developing solution 1).
g-10 g, more preferably 1 g to 5 g.

In addition, as compounds that directly preserve the aromatic primary amine color developing agent, various hydroxylamines, hydroxamic acids described in Japanese Patent Application No. 61-186559, and 6
Hydrazines and hydrazides described in No. 1-170756, No. 61-188742 and No. 61-203253
Phenols described in No. 61-188741, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/or
Alternatively, it is preferable to add various saccharides described in 61-180616.
No. 1-147823, No. 61-166674, No. 61
-165621, 61-164515, 61-
Monoamines described in No. 170789 and No. 61-168159, No. 61-173595, No. 61-1
Diamines described in No. 64515, No. 61-186560, etc., No. 61-165621, and No. 61-169
Polyamines described in No. 789, polyamines described in No. 61-188619, nitroxy radicals described in No. 61-197760, No. 61-186561, and 6
Alcohols described in No. 1-197419, No. 61-19
Oximes described in No. 8987 and No. 61-26514
It is preferable to use the tertiary amines described in No. 9.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
The aromatic polyhydroxy compound described in No. 746,544 may be included if necessary, and addition of an aromatic polyhydroxy compound is particularly preferred.

The color developing solution used in the present invention preferably has a pH of 9 to
12, more preferably 9-1). 0, and the color developer may contain other known developer component compounds.

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

Specific examples of buffering agents 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, 0-
Sodium hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, 5-sulfo-2
-sodium hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (5-potassium sulfosalicylate), and the like. However, the present 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, particularly 0.1 mol/l to 0.4 mol/l.
Particular preference is given to mol/l.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or to improve the stability of the color developer.

As the chelating agent, organic acid compounds are preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.

Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N'N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diamino Bropane tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid,
Ethylenediamine orthohydroxyphenylacetic acid, 2-
Phosphonobutane-1,2,4-)licarboxylic 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.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer.

For example, it is about 0.1 g to 10 g per 1).

Any development accelerator can be added to the color developing solution if necessary. However, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, preparation properties, and prevention of color staining.
"Substantially" means containing less than 2 mA per developer solution (1), preferably not at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 3B-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3,
813,247, etc., p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50137726, JP-A-44-30074, JP-A-44-30074; Quaternary ammonium salts shown in No. 56-156826 and No. 52-43429, etc., U.S. Patent Nos. 2 and 4
No. 94,903, No. 3,128゜182, No. 4,23
No. 0.796, No. 3,253.919, Special Publication No. 1979-
1) No. 431, U.S. Patent No. 2,482,546, No. 2
, 596.926 and 3,582,346, etc., Japanese Patent Publication No. 37-16088, 4
No. 2-25201, U.S. Patent No. 3. 128. 183
Polyalkylene oxides disclosed in Japanese Patent Publication No. 41-1) No. 431, No. 42-23883, U.S. Pat. It can be added accordingly.

In the present invention, any anti-capri agent can be added as required. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic anti-capri agents include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylhensitriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benz Representative examples include nitrogen-containing heterocyclic compounds such as imidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developing solution used in the present invention may contain a fluorescent whitening agent, and the preferable fluorescent brightening agent is a 4°4'-diamino-2,2'-disulfostilbene compound.
The amount added is 0 to 5 g/l, preferably 0.1 g to 4 g/j
It is +.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developing solution of the present invention is 20 to 50°C, preferably 30 to 45°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes. Although it is preferable that the amount of replenishment is small, it is 100 to 1,500 ml, preferably 100 to 800 ml, per one photosensitive material. More preferably 100m
I! , ~400 m1.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment.

The processing method of the present invention can also be used for color reversal processing. The black-and-white developer used at this time is a so-called black-and-white first developer used in the commonly known reversal processing of color photosensitive materials. Various well-known additives that are used in black-and-white developing solutions used in processing solutions for black-and-white silver halide light-sensitive materials can be included in the black-and-white first developer for color reversal light-sensitive materials.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Examples include inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, and methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. be able to.

The processing method of the present invention comprises processing steps such as color development, bleaching, bleach-fixing, and fixing as described above.

Here, after the bleach-fixing or fixing process, processing steps such as water washing and stabilization are generally performed, but after a bath with fixing ability, stabilization processing is performed without substantial water washing. It is also possible to use convenient processing methods.

The rinsing water used in the rinsing step can contain known additives, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
Disinfectants to prevent the growth of various bacteria and algae, anti-fungal agents (eg, isothiazolone, organic chlorine disinfectants, benzotriazole, etc.), surfactants to prevent drying load and unevenness, etc. can be used. Or L, E.

West, “Water Quality Cr1t
eria”, Phot, Sci.

and Eng, +vol. 9.1) 6, page'
Compounds described in 344-359 (1965) and the like can also be used.

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes the dye image is used. For example, a solution having a buffering capacity of pH 3 to 6, a solution containing an aldehyde (for example, formalin), etc. can be used. The stabilizing solution may contain ammonium compounds, metal compounds such as Bi and A1, optical brighteners, chelating agents (e.g. 1-hydroxyethylidene-1,1-diphosphonic acid), bactericides, anti-fouling agents, etc. as necessary. Hardeners, surfactants, alkanolamines, etc. can be used.

In addition, the water washing step and the stabilization step are preferably performed using a multi-stage countercurrent method, and the number of stages is preferably 2 to 4. The replenishment amount is 1 to 50 times the amount brought in from the previous bath per unit area, preferably 2 to 30 times. times, more preferably 2 to 15 times.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
It is preferable to use water that has been deionized to have an Mg concentration of 5 .mu./l or less, water that has been sterilized with halogen, an ultraviolet germicidal lamp, or the like.

In each of the above processing steps for color photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution may occur due to evaporation, especially when the processing amount is small or the opening area of the processing solution is large. It becomes noticeable. In order to correct such tl:A shrinkage of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step flows into a pre-bath having a fixing ability.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of the emulsion layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having a light-sensitive layer on a support, which is composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities; The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally as follows: A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order from the support side. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
) No. 3438, No. 59-1) No. 3440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may contain color mixing inhibitors, ultraviolet absorbers, stain inhibitors, etc. as commonly used.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are
West German Patent No. 1,121,470 or British Patent No. 9
As described in No. 23.045, a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer can be preferably used. Usually, the layers are arranged so that the sensitivity decreases toward the support. Preferably, a non-photosensitive layer may be provided between each halogen emulsion layer.
1) No. 2751, No. 62-200350, No. 62-2
As described in No. 06541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (OH) / low sensitivity green sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL), or B H/B L/C; L/G H/RH/RL, or B H/B L/ They can be installed in the order of GH/GL/RL/RH, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer /C, H/
They can also be arranged in the order of RH/CL/RL. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH may be arranged in this order from the farthest side from the support. can.

Furthermore, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is a silver halide emulsion layer with higher sensitivity than the middle layer. An example is an arrangement consisting of three layers having different photosensitivity, in which a silver halide emulsion layer with a low density is arranged, and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

Any of these layer arrangements can be used in the color photosensitive material of the present invention, but in the present invention, the dry film thickness of all constituent layers of the color photosensitive material excluding the support and the undercoat layer and back layer of the support is 20.0 μm. The following is preferable in order to achieve the object of the present invention. More preferably 18.0
It is less than μ.

These film thickness regulations are determined by the color developing agent that is incorporated into these layers of the color photosensitive material during and after processing. By making a big impact. In particular, the increase in color of magenta, which is thought to be caused by the green-sensitive color layer, is larger than the increase in color of other cyan and yellow colors.

It should be noted that the lower limit value in the film thickness regulation is desirably reduced within a range that does not significantly impair the performance of the photosensitive material based on the above regulations, and is based on the total drying of the constituent layers excluding the support of the photosensitive material and the undercoat layer of the support. The lower limit of film thickness is 12. θμ, and the lower limit of the total dry film thickness of the constituent layers provided between the photosensitive layer closest to the support and the undercoat layer of the support is 1.0μ.

Further, the film thickness may be reduced in either the photosensitive layer or the non-photosensitive layer.

The occurrence of these bleaching edge blurs and stains is thought to be due to the green-sensitive color layer, and the color increase in magenta is greater than the color increase in other yellow and cyan colors.

Note that the lower limit in the film thickness specification is not limited because it is desirable to reduce the film thickness within a range that does not significantly impair the performance of the photosensitive material for the above reasons. It may be any of the photosensitive layers.

The film thickness of the multilayer color photosensitive material in the present invention is measured by the following method.

The sensitive material to be measured is stored under conditions of 25° C. and 50% RH for 7 days after preparation. First, measure the total thickness of this sensitive material, then remove the coated layer on the support, measure the thickness again, and use the difference to calculate the total thickness of the coated layer of the above-mentioned sensitive material excluding the support. The film thickness shall be . This thickness can be measured using, for example, a film thickness measuring device (Anritus) using a contact type piezoelectric transducer.
Electric Co.

Ltd., K-402B 5tand, ). Note that the coating layer on the support can be removed using an aqueous sodium hypochlorite solution.

Next, using a scanning electron microscope, take a cross-sectional photograph of the above-mentioned sensitive material (magnification is preferably 3.000 times or more), measure the total thickness on the support and the thickness of each layer, and calculate the previous film thickness. The thickness of each layer can be calculated by comparing it with the total thickness measured by the measuring device (absolute value of the actual thickness).

Swelling rate of the photosensitive material of the present invention [(equilibrium swelling film thickness at 25°C, H, 0 - dry total film thickness at 25°C, 55% RH/2
Dry total film thickness at 5°C and 55% RH) xloo) is 50~
200% is preferable, 70 to 150% is more preferable,
If the swelling ratio deviates from the above value, the amount of color developing agent remaining will increase, and this will have an adverse effect on photographic performance, image quality such as desilvering properties, and film properties such as film strength.

Further, the swelling rate of the photosensitive material of the present invention is defined as the swelling rate T'A, which is defined as the time taken to reach 90% of the saturated swollen film thickness in a color developing solution (38°C).
Preferably, Vl is 15 seconds or less, more preferably T'A is 9 seconds or less.

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

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

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

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), Arashi 17643
(December 1978), pp. 22-23, '1. Emulsion preparation and
types)” and the same Na18716 (1979
January 2016), 64B pages, Graphic "Physics and Chemistry of Photography", published by Paul Montell (P, Glafkide)
s.

Chemic et Ph1sique Pho
tographique Paul Montel
+1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F. Duffin, Phot
graphicEIllusion Chemist
ry (Focal Press 1966)),
"Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L. Zelikman at a
t.

Making and Coating Photo
rapic Emulsion + Focal P
ress + 1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3.655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gatz, Photographic Science and Engineering CCutoff, PhotographicSc.
engineering), 1st
4, pp. 248-257 (1970); U.S. Patent No. 4
, 434°226, 4,414,310, 4,
433.048, 4,439,520, and British Patent No. 2,1) 2,157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may have a silk-like structure, or silver halides of different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Section 17.
643 and the same 18716, and 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 descriptions are shown in the table below.

Species 1 Chemical sensitizers 2 Sensitivity enhancers 3 Spectral sensitizers, supersensitizers 4 Brighteners 5 Antifoggants and stabilizers 6 Light absorbers, filter dyes UV absorbers 7 Anti-stain agents 8 Dye image stabilization Agent 9 Hardener 10 Binder 1) Plasticizer, lubricant 12 Coating aid, surface active agent 13 Static inhibitor RD 17643 23 pages 23-24 pages 24 pages 24-25 pages 25-26 pages 25 right column page 25 Page 26 Page 26 Page 27 Page 26-27 Page 27 RD18716 Page 648 Right column Same as above Page 648 Right column - Page 649 Right column Page 649 Right column - Page 649 Right column - Page 650 Left column Page 650 Left - Right column Page 651 Left Column 650 True right column Same as above Same as above Various color couplers can be used in the present invention, and specific examples thereof include the above-mentioned RDN1) 7643,
It is described in the patent described in .

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,326
, No. 024, No. 4.401,752, No. 4,248
．． No. 961, Special Publication No. 58-10739, British Patent No. 1
．． No. 425,020, No. 1,476.760, U.S. Patent No. 3. 973°968, 4,314.023, 4.51). 649, European Patent No. 249.473
Those described in No. A etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, 4.351. No. 897 1. European Patent No. 73,636, U.S. Patent No. 3.061,432,
No. 3,725.064, RD 24220 (1
(June 984), JP-A No. 60-33552, RD
Na24230 (June 1984), JP-A-60-4
No. 3659, No. 61-72238, No. 60-3573
No. 0, No. 55-1) No. 8034, No. 60-185951
No., U.S. Patent No. 4,500,630, U.S. Patent No. 4,540°654, U.S. Patent No. 4,556,630, WO (PCT) 8
Particularly preferred are those described in No. B104795.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,14/6.396, No. 4.228,233
No. 4,296,200, No. 2,369,929, No. 2,801.171, No. 2,772.162,
2.895.826, 3,772.002, 3,758゜308, 4,334,01), 4
, 327.173, West German Patent Publication No. 3.329,72
No. 9, European Patent No. 121,365A, 249°45
3A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,33
No. 3,999, No. 4,753,871, No. 4,451
, No. 559, No. 4.427.767, No. 4,690,
No. 889, No. 4.254.212, No. 4,296,1
99, JP-A No. 61-42658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in RD No. 17643, Section ■-G, U.S. Pat.
．． 163,670, Japanese Patent Publication No. 5739413, U.S. Patent No. 4.004,929, U.S. Patent No. 4,138,258,
The couplers described in British Patent No. 1.146°368 are preferred, and the couplers that compensate for unnecessary absorption of color-forming dyes by the fluorescent dye released during coupling, as described in U.S. Pat. No. 4,774.181; It is also preferred to use couplers having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in U.S. Pat. No. 4,777.120.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, 570, European Patent No. 96.570, and German Patent Publication No. 3.234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820;
It is described in 4,367.282, 4,409.320, 4,576.910, British Patent 2,102,173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
No. 57-154234, No. 60-184248, No. 63-37346, U.S. Patent No. 4,248.962
No. 4°782.012 is preferred.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097.140;
Those described in JP-A No. 2,131,188, JP-A-59-157638, and JP-A-59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4.1.30,427, U.S. Pat. No. 4.283.472,
Long equivalent couplers described in JP 4,338,393, JP 4,310,618, etc.
DIR redox compound releasing coupler, DIR coupler releasing coupler, D as described in JP-A-62-24252 etc.
IR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173.30
2A, a coupler that emits a dye that recovers color after separation, RD G1) 449, 24241, JP-A-61-20
Bleach accelerator releasing couplers described in US Pat. , 774.181, etc., which emit a fluorescent dye.

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

Examples of high-boiling point solvents used in the oil-in-water dispersion method are described in U.S. Patent No. 2,322,027, etc.; Specific examples of a-containing solvents include fucuric acid ester R (
Dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate,
bis(2゜4-di-t-amylphenyl) phthalate,
bis(2,4-di-t-amyl phenyl) isophthalate, bis(1,l-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl Diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tryptoxyethyl phosphate, trichloropropyl phosphate, di-2
-ethylhexyl phenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides 1 (N,N-diethyldodecaneamide, N,N-diethyl laurylamide,
N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-
di-tert-amylphenol, etc.), aliphatic carboxylic acid esters W4 (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N- Diptyl-2-
butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. Further, 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, 2- Examples include ethoxyethyl acetate and dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation can be found in U.S. Pat.
41,230, etc.

These couplers can also be impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO8B100723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

The present invention can be applied to various color photosensitive materials. It is particularly preferable to apply the present invention to color negative films for general use or movies, and color reversal films for slides or televisions.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, Arashi 17643, page 28, and Kaimagai 18716, 64
It is described from the right column on page 7 to the left column on page 648.

(Example) The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these.

Example l On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of the photosensitive layer) The numbers for each component indicate the coating amount in g/rrl, except for silver halide, colloidal silver and couplers, the amount in g/rd of silver and the sensitized The dyes are expressed in mole units per mole of silver halide in the same layer. The numerical value written in parentheses at the end of each layer indicates the film thickness [unit: μ].

1st layer: Antihalation layer black colloidal silver Silver coating amount 0.20 Gelatin v-i V-2 pd-I olv-I olv-2 olv-3 2nd layer: Intermediate layer 2, l 5 0, l 0 0 .20 0,05 0, Ol O,01 0,08 (2,1) Fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating amount 0.15 Gelatin 1.00Cpd-
20,20 (1,O') Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (Agr 10.0 mol%, internal high Ag
L type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%,
14
Face piece particles) Silver coating 1 0.40 Gelatin 2.00ExS-
19, oxto-'mol ExS-23, oxto-'mol ExS-30, axto-'mol ExS-40,5xio-'mol ExC-10,33 ExC-20,009 ExC-30,023 ExC-60,14 (2,3) 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Ag1 16 mol%, internal height A, GL type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate shaped particles, diameter/thickness ratio 4°0) Silver coating amount 0.80 Gelatin 1.
30ExS-14,oxto-'ExS-21,5xlO-'ExS-30,4xto-'ExS-40,4X10-' ExC-30,05 ExC-40,10 ExC-60,08 (1,5) 5th J ! : Third red light emulsion layer silver iodobromide emulsion (A g I 10.-6 mol %, internal high Agl type, equivalent sphere diameter 1.2 μ, coefficient of variation of equivalent sphere diameter 2
8%, plate-like particles, diameter/thickness ratio 6゜0)
Silver coating 1 1.10 gelatin
1.20ExS-12,5X 10-'ExS-20,7X10-'ExS-30,3xto-' ExC-40,07 ExC-50,06 Solv-10,12 Solv-20,1,2 (1,6 ) 6th layer: Intermediate layer gelatin 1.30Cpd-
40,10 (1,1) 7th layer: First green-sensitive emulsion layer Silver iodobromide emulsion (AgllO, 0 mol%, internal high Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 14%) , 14
(Hedron grain) Silver coating amount 0.20 Silver iodobromide emulsion (Ag1 4.0 mol%, internal high Agl type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, 14
Face piece particles) Silver coating amount 0.10 Gelatin 1.40ExS-
55xto-'ExS-62X10-'IExS-71XIO-' ExM-10,21 ExM-60,31 ExM-20,10 ExM-50,03 Solv-10,20 Solv-50,03 (1,9) 8th Layer: Second green-sensitive emulsion layer Silver iodobromide emulsion (Ag1 10 mol%, internal high iodine type,
Equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 3.0) Silver coating amount 0.50 Gelatin 0.45ExS-
54,5xto-'ExS-61,5xto-'EXS-70,9XlO-' ExM-10,09 ExM-30,01 Solv-10,15 Solv-50,03 (0,8) 9th N: Intermediate layer gelatin 0.50 (0,4
) 10th layer: 3rd green emulsion layer silver iodobromide emulsion (AgT 10.0 mol%, internal high Ag
L type, equivalent sphere diameter 1.2μ, coefficient of variation of equivalent sphere diameter 28%,
Plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 1.20 Gelatin 1.40ExS-
52,4xio-'ExS-61,oxto-'ExS-71,0XIO-' ExM-30,01 ExM-40,14 ExM-10,04 ExC-40,005 Solv-10,2 (1,8) No. 1) Layer: Yellow filter layer Cpd-30,05 gelatin 0.503o1v
-10,10 (0,5> 12th layer: intermediate layer gelatin 0.50Cpd-
20,t.

(0,5) 13th layer: first blue-sensitive emulsion layer silver iodobromide emulsion (Ag1 10 mol%, internal high Agl type,
Equivalent sphere diameter 0.7°μ, coefficient of variation of equivalent sphere diameter 14%, 14
Silver coating 1 0.15 Silver iodobromide emulsion (Ag 14.0 mol%, internal high Agr type,
Equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particles) i 艮Amount of coating 0, 08 Gelatin 1.20ExS-
84,5xto-' ExY-10.62 ExY-20,02 Solv-10,20 (1,9') 14th layer; 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Ag! 19.0 mol%, Internal height Ag
Type I, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 16%,
Tedecahedral particles) Silver coating amount 0.30 Gelatin 0.30ExS-
83.0 0.20 Gelatin 0.36 (0,4
) 16th rfi: 3rd blue emulsion layer silver iodobromide emulsion (Ag! 14.0 mol%, internal high Ag
L type, equivalent sphere diameter 1.5 μ, coefficient of variation of equivalent sphere diameter 28%,
Plate-shaped particles, diameter/thickness ratio 5.0) Silver coating 9 1.20 Gelatin 0.90ExS-
81,5xto-' ExY-10,20 Solv-10,07 (1,3) 17th layer: 1st protective layer gelatin 1.80uv-t
o. 1 OUV-20,2
0 Solv-10,01 Solv-20,01 (1,7) 18th layer: 2nd protective layer Fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating amount 0.18 Gelatin polymethyl methacrylate particles (diameter 1 .5μ) pd xC Hz xC 0°V-1 0°1°(2,1) COOCH.

X/y=7/3 (Mtanshi xM xC H xC xC CI! H.

xM l 1xY-2 xS xS-2 Ils zHs C@Hs xM xS-3 xS xS-5 xHS xS xS xS pd ! pa C! H8 Cb Ht! (n) olv-1 olv o lv LL+sMu QOH pd-5 CH.

To1! 1 C1F+ySOz NHCHz C1'h C1h 0
CH2CHz N' (CHJi+1 CH yo CH3 (hC summer (, C0NH CH.

Cjb “CH30□CHz C0NHCH.

At this time, the dried film thickness of all coating layers except the support and the undercoat layer of the prepared sample 101 was 23.degree. 5.mu.m.

The prepared sample was cut and processed into 35IIm, wedge exposed to internal light (light source color temperature 4800'K), and processed using a cine-type automatic processor according to the processing recipe shown below. However, the samples to be evaluated for performance were subjected to imagewise exposure until the cumulative replenishment amount of the color developer reached three times the volume of the mother solution tank, and then the samples were processed.

Processing process Processing time Processing temperature Replenishment amount 09 valve capacity Color development 3 minutes 15 seconds 37.8℃ 23tal 1
01 bleaching 40 seconds 38.0℃
5I1) 151 fixed 1 minute 30 seconds 38.
0℃ 3 times 1) 01 water washing (1) 30 seconds 38.0℃
-151 water washing (2130 seconds 38.0℃ 30m
j! 51 Stable 30 seconds 38.
0℃ 20m151 drying 1 minute
55℃ *Replenishment amount is 35m-width 1. Quantity per m Washing method: Countercurrent method from (2) to (1) Note that the amount of developing solution carried into the bleaching process and the amount of fixing solution carried into the washing process are per 1 meter length of photosensitive material with a width of 35 m5. They were 2.5 rne and 2.0 m12, respectively.

Further, the crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below.

(Mother solution developer) diethylenetriaminepentaacetic acid l-hydroxyethylidene 1, l-diphosphonic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfate 2-methyl-4-[N-ethyl Ru-N-(β-hydroxy Mother liquor (g) 1.0 3.0 Replenisher (g) 1.1 3.2 4.0 30.0 1.4 1.5 ■ 2.4 4.5 4.9 30.0 ethyl) aminocoaniline sulfate add water H (bleach solution) 1.3-propylene diamine Ferric ammonium tetraacetate water salt 1.3-propylene diamine Tetraacetic acid ammonium bromide ammonium nitrate Acetic acid (98χ) add water pH (adjust 7n77water (27χ)) (Fixer) Ethylenediaminetetraacetic acid di ammonium salt 1.01 1.01 10.05 10.10 Mother liquor (g) Replenisher (g) 144.0 206.0 2.8 4.0 84.0 120.0 30.0 41.7 0.80 mole 1.16 mole 1, OR1,01 4,03,2 Common to mother liquor and replenisher (g) 1.7 Ammonium sulfite 14. .

Ammonium thiosulfate aqueous solution 340.0ml (70ml)
0g80 Add to water 16olpH7
,0 (washing water) Common tap water for mother liquor and replenisher was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IRA-4 manufactured by Rohm and Haas).
Water was passed through a hotbed column packed with 00) to reduce the concentration of calcium and magnesium ions to 3/l or less, and then 20/l of sodium isocyanurate dichloride and 150/l of sodium sulfate were added. .

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

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (37%) 1.2ml Surfactant 0. 4(C+ol(it)
O-(CHgCHgO)-+eH) ethylene glycol 1. 0 Add water
1. These samples obtained by ORp H5,0-7,0 treatment are designated as A-1.

The concentrations of these samples were measured, and the Da+in values measured with green light (G light) were read from the obtained characteristic curves.

Then, the bleaching solution mother liquor pr+=s, o, the replenisher pH=4.3; the mother liquor pH=6. pH of L replenisher = 5.
5, and each was treated according to the treatment method of Group A. However, the pH can be adjusted using ammonia water (27
%) were used to make individual adjustments. These treated samples are designated as B-1 and C-1, respectively.

Furthermore, as shown in Table 1, the concentration of acetic acid in the bleaching solution is 1.20 mol for the mother liquor, 1.75 mol for the replenisher;
．． 80 mol, replenisher 2.62 mol; mother liquor 2.00 mol, replenisher 2.91 mol; mother liquor 2.50 mol, replenisher 3.64 mol, and the pH of each is A-1-C. -1
Change in the same way as A-2 to A-5 to C-2 to C-5.
The treatments up to this point were carried out in the same manner as described above.

In addition, the bleaching solution was changed to the following processing solution formulation, the bleaching time was 390 seconds, the processing temperature was 38°C, and the amount of replenisher was 25ml.
/35m width and 1m sample, and the processing was carried out without changing anything else.

(Standard bleaching solution) Mother solution (g) Replenisher (g) Sodium ferric ethylenediaminetetrasentate trihydrate Ethylenediaminetetraacetic acid disodium chloride Ammonium bromide Ammonium nitrate Aqueous ammonia (27χ) Add water to pH 100,0!20 .0! 0.0 140.0 30.0 6.5am! 1.OI! ! 6.0 1). 0 160.0 35.0 4.0L1) 1, Of 5.7 The concentration of the above-mentioned treated sample and all the samples of 8-1-C-5 was measured using G light as in A-1. , Dmin value was read.

These obtained Dmin values were determined by using ethylenediaminetetraacetic acid Fe(DI)ti salt in the bleaching solution at 38°C23
The Dmin value of the sample obtained after processing for 90 seconds was used as a reference (the actual measured Dmin value of the sample at this time was 0°62), and comparisons were made between the samples. The results are shown in Table 1.

Chapter 1 Table The present invention is shown within the general frame.

As a result, the acetic acid concentration of the mother liquor of the bleaching solution of the present invention was reduced to 15
It can be seen that Dmin(a) is low when the pH of the bleaching solution is 20 mol/l or more. In particular, it can be seen that the Dmin value is significantly low when the pH of the bleaching solution is 5.0 or less.

Furthermore, the pH of the mother liquor of the bleaching solution is 3.7, and the pH of the replenisher is
Sample 101 was treated in the same manner, except that the respective treatment solutions were prepared by using aqueous ammonia (27%) to obtain the same result as A-1.

Next, using the previously treated samples A-1 to C-5, an attempt was made to test the increase in stain in the uncolored areas when the samples were stored after the treatment under the following conditions.

dark)! Thermal conditions: 80°C, 70% RH D in green light of unexposed areas before and after storage under the above forced conditions for 17 days
Measure sin, △D, (Dmin after the test) - (Dm before the test)
in) was calculated to evaluate the stain. Second result
Shown in the table.

No. table The present invention is shown within the general frame.

From the results in Table 2, it is clear that when the treatment is performed with a bleaching solution that meets the requirements of the present invention, the increase in staining after treatment is small. In particular, it is remarkable that the increase in stain is small when the pH is low.

Example 2 Using Sample 101 prepared in Example 1, the organic acid acetic acid used in the composition of the bleaching solution described in Example 1 was replaced with monochloroacetic acid, propionic acid, monochloropropionic acid, butyric acid, and malon. Acid and citric acid/acetic acid-A (molar ratio)
Further, from the results shown in Table 3 above, it can be seen that the organic acids of the present invention having a pKa of 2 to 5 are excellent. Among the organic acids used, monobasic acids are preferred, and among them, acetic acid is the best. Furthermore, trichloroacetic acid and pyridine whose pKa is outside the range of 2.0 to 5.0 are clearly Ds
It can also be seen that +in is high and is not suitable for the purpose of the present invention.

For comparison, trichloroacetic acid and pyridine were used, the concentrations were 1.80 mol/II for the mother liquor and 2.62 mol/l for the replenisher, and the pH was 4.0 for the mother liquor and 3.0 for the replenisher.
．． 2 using ammonia water (27%) and sulfuric acid (1N solution), and exposed as described in Example 1.
The processing method was also the same. The concentration of the obtained treated sample was measured, and the oxidizing agent in the bleaching solution was replaced with EDTA-F e (In) 1M salt according to the method of Example 1 at a pH of 6°0 and a bleaching temperature of 38°C. Evaluation was performed based on Dsin of the treated sample. The results are shown in Table 3.

Example 3 On a subbed cellulose triacetate film support,
Sample 301, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/n (units). However, for silver halide and colloidal silver,
The coating amount expressed in glcd units in terms of silver and the coating amount of the sensitizing dye are expressed in mole units per mole of il halide in the same layer.

(Sample 301) 1st layer (antihalation layer; film thickness 1.2μ) black colloidal silver silver 0.18 gelatin
1.50 Second layer (intermediate layer; film thickness 1.
7μ) 2.5-di-t-pentadecylhydroquinone 0.18EX-1
0,07 EX-30,02 EX-120,002 U-10,06 0-20,08 U-30,10 HBS-10,10 1) BS-20,02 Gelatin 1.40 3rd N (
First red emulsion layer; film thickness 1.5μ) Emulsion A
Silver 0.25 emulsion B
Silver 0.25 Sensitizing dye 1 6.9
X10-'sensitizing dye 1) 1.8Xl
O-'sensitizing dye III 3.1X
IO-'EX-20,335 EX-100,020 tl B S -10,060 Gelatin 1.20 4th layer (
2nd red-sensitive emulsion layer; film thickness 2.0μ) Emulsion G
Silver 1. 0 sensitizing dye +
5.1X10-S Sensitizing Dye II
1.4XlO-'sensitizing dye III
2.3X10-'EX-20,400 EX-30,050 EX-100,015 HBS-10,060 Gelatin 1.55 5th layer (
Third red-sensitive emulsion layer; film thickness 2.4μ) Emulsion D
Silver 1.60 sensitizing dye!
5.4xlO-'sensitizing dye■
1.4X10-' sensitizing dye I1) 2
．． 4X10-'EX-30,010 EX-40,080 EX-20,097 8BS-10,22 HBS-20,10 Gelatin 1.85 6th layer (
Intermediate layer; film thickness 1.0 μ) EX-50,040 HB S -10,020 Gelatin 1.15 7th layer (
1st green emulsion; film thickness 1.5μ) Emulsion A
Silver 0.15 emulsion 8
1) 0.15 sensitizing dye V 3.
0xlO-' Sensitizing dye Vl 1.0
xlO-'sensitizing dye ■ 3.8X10
-' [EX-60,100 EX-140,250 EX-10,021 EX-70,030 EX-80,025 1) BS -10,300 1) BS-30,010 Gelatin 0.90 8th layer (
2nd green-sensitive emulsion layer; film thickness 1.0μ) Emulsion C Silver 0.45 Sensitizing dye V 2. lXl0-'Sensitizing dye Vl 7.0xlO-'Sensitizing dye■ 2.6X10-'EX-60
,060 EX-140,053 EX-80,018 EX-70,026 1) B S -10,160 1) B S -30,008 Gelatin 0.70 9th layer (
Third green emulsion layer; film thickness 2.2μ) Emulsion E
Limit 1.2 Sensitizing dye V
3.5X10-' sensitizing dye Vl 8
．． 0X10-' Sensitizing dye ■ 3.0X
10-'EX-130,015 EX-1) 0,100 EX-10,025 8BS-10,25 HBS-20,10 Gelatin 1.75 1st O layer (yellow filter layer; film thickness 1.θμ) Yellow colloid Silver 0.05EX-50,08 HBS-10,03 Gelatin 1.10 1st) layer (first blue emulsion layer; film thickness 2.0μ) Emulsion A
Silver 0. θB emulsion 8
1B10.07 Emulsion F
1! 0.07 sensitizing dye ■ 3.5X
lO-'EX-90,721 8X-80,042 HBS-10,28 Gelatin 1.25 12th layer (second blue emulsion layer; film thickness 1.1μ) Emulsion G
Silver 0.45 sensitizing dye■
2.1X10-'EX-90,154 2X-100,007 HBS-10,05 Gelatin 0.95 13th layer (third blue emulsion layer; film thickness 1.2μ) Emulsion H silver 0.7
7 Sensitizing dye ■ 2.2X10-'EX-
90,20 HBS-10,07 Gelatin 0.90 14th layer (first protective layer; film thickness 1.5μ) emulsion!
Silver 0.5U-40,1) U-50,17 HBS-10,05 Gelatin 1.30 15th layer (second protective layer; film thickness 2.0 μm) Polymethyl acrylate particles (diameter approximately 1.5 μm) 0 .543-1
0.20 gelatin
1.25 In addition to the above ingredients, l and a surfactant were added to each layer.

Gelatin hardener H X X-2 H X X Cx X X H H Hs X-7 X LX C snow Hs C proverb H% Cx Hs 03Os・ X-13 X-14 U-4 Sensitizing dye■ Sensitizing dye■ Sensitizing dye V x:y-TO:30 (-mountain V B.S. to licresyl phosphate tsu Bu Chilphthalate Sensitizing dye■ Sensitizing dye■ Exacerbating pigment■ (cu.) a So- (CHJ4SOs EtoN (Ci I(s)iS ■１ ■ ■ Hs C1h=CH-5ot-CH.

C0N)! -CH□ CH,=CH-3o□-CH* -CON H-CH*
The dried film thickness of all the constituent layers of sample 301 prepared except for the support and the undercoat layer of the support was 23.3μ. This sample 401 was cut and processed into 35-sized pieces, exposed to the same 1H light as in Example 1, and subjected to the following treatment. However, the sample was processed after imagewise exposure was performed until the cumulative replenishment amount of the color developing solution reached three times the volume of the mother liquor tank.

Processing method step Processing time Processing temperature Color development 23330 seconds 38℃ bleaching 40 seconds 38℃ bleach-fixing (ll
40 seconds 38℃ bleach fixing (2140 seconds 38
℃ Water washing (1) 30 seconds 38℃ Water washing +21 30 seconds 38℃ Stable 30 seconds 38℃ Drying 1 minute 55℃ 2) It is a counter-current method to the tank (1), and the overflow replenishment amount of bleaching solution 1 Tank capacity 25mff1 10 1 5egl 4 1) 47! All of the I1 solution was introduced into bleach-fixing (2).

In the above process, the amount of bleach-fix solution carried into the washing process was 2 ml per length of the photosensitive material In, which had a width of 35 m/m.

(Color developer) Same as the color developer in Example 1 (Bleach solution) Same as Bleach solution A-3 in Example 1 (Bleach-fix solution) Mother liquid axis) Replenisher (g) Ethylenediaminetetraacetic acid dibasic 50.0 Iron ammonium dihydrate ethylenediaminetetraacetic acid 5.0 25.0
gThorium salt ammonium sulfite 12.0 20.
0g ammonium thiosulfate aqueous solution 290.0m132
0.0 mA (700 g m0 Ammonia water (27χ) Add water and H 6, (hl 1.01 6.8 15.0 mj! 1.01 8.0 (Washing liquid) Same as the washing liquid of Example 1 ( Stable solution) Common to mother liquor and replenisher solution (Unit g) Formalin (37χ) 2. Osj polyoxyethylene-p-mono 0.3 Nyl phenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid disu 0.05 Thorium salt water Plus 1.01p H5
, 8-8, 0 The obtained treated sample is designated as D.

Next, 1,3-DTPA-Fe (Iff
) was replaced with an equimolar amount of 1,4-butylenediaminetetraacetic acid iron (m) complex salt to prepare a bleaching solution, and the treatment was carried out in the same manner as above. The obtained treated sample is designated as E.

In addition, 1.3-DTPA-Fe (Ill) was converted into N-(2
-acetamido)iminodiacetic acid iron(III) complex salt was substituted in an equimolar amount, and the treatment was carried out in the same manner as above. The obtained treated sample is designated as F.

Furthermore, using the standard bleaching solution of Example 1, the treatment time and treatment temperature were the same, and the replenisher amount was 25 mA/sample 35 length/1 m.
Processing was performed as follows.

The sample obtained by performing the above treatment is designated as G.

Subsequently, a standard bleaching solution was used and the treatment time was extended to 6 minutes and 30 seconds. The obtained sample is designated as ■1.

Subsequently, the pH of the reference bleaching solution was adjusted to the pH of the bleaching solution treated with D of this example, and the treatment was carried out for the same treatment time. The obtained treated sample is designated as I. Furthermore, D
The p)I of the bleaching solution used in the treatment was adjusted to 6.0. The obtained sample is designated as J.

Each of these treated samples of DJ was subjected to concentration measurement, and the Dmin value measured with green light was read from the characteristic curve. Using the Dmin value (=0°60) of Sample I as a reference, the difference (80min) was calculated. The results are shown in Table 4.

From the results shown in Table 1, it is clear that when the oxidizing agent having a high redox potential of the present invention is used in a low pH solution, the increase in Dmin is small. On the other hand, with EDTA/Fe(III), which has a lower redox potential than the oxidizing agent of the present invention, the pH
It can be seen that low or high pH does not result in bleach fog; however, when an oxidizing agent with a high redox potential is used in a high pH bleaching solution, significant bleach fog occurs. It can be seen that Dmin is high.

Next, the stain increase during image storage using the processing solution described in Example 1 for the above sample was examined under the same conditions. Evaluation was performed using the same method. The results are shown in Table 5.

Table 5 was carried out. The amount of residual silver in these E-treated samples was determined by fluorescent X-ray method. These quantitative results are shown in Table 6.

From the results shown in the above table, it can be seen that the bleaching solution using the oxidizing agent having a high redox potential of the present invention is very superior in that there is little increase in staining in uncolored areas during image storage.

At this time, the swelling speed T〃 in treatment E was 8 seconds, and the swelling rate was 1) 5%.

Next, sample 301 was uniformly exposed to give a gray density of 1.5, and the bleaching solution and treatment time were changed in the same manner as in the method described above. Oxidizing agent having a high redox potential of 150 mV or more, l,3-DTPA•Fe (III), 1. 4
-Butylenediaminetetraacetic acid/Fe(m)li salt and N-
(2-acetamido)iminodiacetic acid pe (m)if
It can be seen that the salt exhibits good desilvering properties. On the other hand, EDTA-F e (III) with a low redox potential has p
Although the desilvering properties are significantly inferior when H is 3.7 or 6.0, it is observed that the desilvering properties are improved by increasing the bleaching time. From the above, the use of the oxidizing agent with a high redox potential of the present invention in a low-pH bleaching solution is effective without increasing bleach blade bristle or staining, and in addition, it is convenient for desilvering. It can be seen that this allows for faster processing.

Example 4 Using Processes D, E, F, and H in which the bleach solution was changed in Example 3, sample 301 was given the white circle wet exposure described in Example 1, and then the volume of the mother liquor tank for color development was increased. The imagewise exposed samples were processed until 3 times the volume was refilled before processing of the samples described above.

Immediately after the treatment was completed, the concentration was measured and its characteristic curve was obtained. After the concentration measurement was completed, these samples were immersed in a 5% aqueous solution of red blood salt and treated at 30° C. for 5 minutes under air conditioning. Thereafter, these samples were washed with running water for 5 minutes and dried, and then the concentration was measured again to obtain a characteristic curve.

From these characteristic curves, it can be seen that the red light (
R) concentration on the characteristic curve measured with 1. 0, read the density (DI) at the same exposure amount on the R characteristic curve before red blood salt aqueous solution treatment, and use these values to determine what is called defective color recovery (reduction of cyan dye into leuco dye). (concentration decrease due to change in) is D%= (D, ・/
l. 0) Calculated by x 100. The results are shown below.

Table 7 As a result of the above table, even if the oxidizing agent having a high redox potential of the present invention is treated in a low pi-1 bath, the oxidizing agent having a comparatively low redox potential can be treated for a long time in a pH 6.0 bath. It is clear that the results are the same as those obtained when time processing is performed, and it can be seen that no defective color recovery occurs.

Example 5 The film thickness of each constituent layer of sample 101 prepared in Example 1 was changed by simply changing the amount of gelatin as shown in Table 8, and other emulsion types, compounds used in each layer, and their coating were applied. A sample was prepared using exactly the same amount as sample 101. However, the ratio of hardening agent H-1 to the amount of gelatin was that of sample 101.
Matched to the same. For each of these prepared samples, there was no particular problem in the coated surface condition of the prepared samples even if the amount of gelatin applied was changed.

These prepared samples were cut and processed into 35 nm, exposed to light as described in Example 1, and processed in accordance with the processing method described in Example 3. However, the p of the mother liquor of the bleaching solution
H is 5.0, the DH of the replenisher is 4°3, and ammonia water (2
7%).

The density of the obtained treated sample was measured, and the Dmin value measured with green light of the characteristic curve was read.

Furthermore, the oxidizing agent described in Example 1 was added to EDTA/Fe
(III), bleaching time was 390 seconds using a bleaching solution with a pH of 6.0, and sample 1 was used with a standard bleaching solution at a processing temperature of 38°C.
D obtained by carrying out the treatment of 01 and carrying out the same concentration measurement
(2) Using the in value as a reference, the difference ΔDs+in was determined, and the film thickness and Dmin of the photosensitive material were investigated. Incidentally, the actual value of Dmin of sample 101 treated with the standard bleaching solution was 0.64. The results are also shown in Table 8.

From the results in Table 8, it is clear that Dsin is reduced by reducing the dry film thickness of all constituent layers except the support and the undercoat layer of the support.

(Effect of the invention) Images with low Dsin can be obtained by using an oxidizing agent with a redox potential of 150 mV or more in the desilvering process and treating with a bleaching solution containing 1.2 mol/l or more of an acid with a pKa of 2 to 5. Moreover, even during long-term storage of this image, it is possible to perform rapid processing with less staining in unexposed areas and excellent desilvering.

In particular, when the bleaching solution has a pH of 5.0 or less, it is possible to carry out treatments with remarkable effects.

Claims (2)

[Claims] (1) After imagewise exposure of the silver halide color photographic light-sensitive material,
In a processing method in which a color developing treatment is performed with a color developing solution containing an aromatic primary amine color developing agent, and then a bleaching treatment is performed with a bleaching solution, the bleaching solution has an oxidation-reduction potential of 150m.
1.2 mol/of an oxidizing agent of V or more and an acid of pKa 2 to 5
A method for processing a color photographic material containing silver halide of 1 or more. (2) The method for processing a silver halide color photographic material according to claim (1), wherein the pH of the bleaching solution is 5.0 or less.