JPH01953A - Processing method for silver halide color photographic materials to improve color restoration defects and cyan stains - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically, it is applicable to silver halide color photographic light-sensitive materials with high sensitivity and high silver content. The present invention relates to a method for processing a silver halide color photographic light-sensitive material, which improves defective color recovery of dyes and provides more stable photographic performance.

[Background of the Invention] Conventionally, high-sensitivity color photographic materials based on silver iodide or silver iodobromide emulsions, particularly color reversal photographic materials and color negative photographic materials using emulsions with a high silver content, have been produced using amino acid. When processing with a processing solution using a polycarboxylic acid ferric complex salt as a bleaching agent, there are disadvantages in that desilvering failure occurs and bleaching takes a long time.

As a means to speed up the desilvering process, which requires a long time, it is possible to contain a ferric aminopolycarboxylic acid complex salt and a thiosulfate as a fixing agent in one bath, as described in German Patent Box 866, 605. It is known to process with a bleach-fix solution.

However, in the above bleach-fix solution, the oxidizing power of the ferric aminopolycarboxylic acid complex is inherently weak, and the coexisting preservative sulfite and fixing agent thiosulfate are reducing agents. , has the function of further weakening the oxidizing power of the ferric aminopolycarboxylic acid complex salt, and as a result not only reduces the desilvering performance, but also easily converts the cyan dye formed by color development into a leuco dye, and It also lacks the ability to develop leuco dyes and has the problem of poor color reproduction, which causes a serious deficiency in color reproduction.

The above phenomenon becomes even more noticeable over time when a photosensitive material is continuously processed over a long period of time.

As a result of repeated studies on the above-mentioned problems, the present inventors have found that the above-mentioned poor color restoration is caused by the use of aminopolycarboxylic acid ferric complex salts and aminopolyphosphonic acid as bleaching agents in the bleach solution or bleach-fix solution in the desilvering process. This is a problem that commonly occurs when using ferric complex salts, especially aminopolycarboxylic acid or aminopolyphosphonic acid, which is produced by its own reduction as a result of the ferric complex salt of aminopolycarboxylic acid or aminopolyphosphonic acid acting as an oxidizing agent. It has also been found that the accumulation of ferrous complex salts (n ions) of aminopolyphosphonic acid in processing solutions or sensitive materials poses a particularly serious problem.

It has also been found that the accumulation of ferrous complex ions depends on the IIH of the bleach solution or bleach-fix solution, and the higher the 1)H, the more likely the formation of ferrous complex ions occurs. Furthermore, the formation of ferrous complex ions occurs not only due to the decomposition of the ferric complex salt of aminopolycarboxylic acid or aminopolyphosphonic acid itself, but also when a bleach-fix solution is used. The sulfite contained as an agent also reduces the ferric complex salt to produce ferrous complex ions.Also, by processing a photosensitive material with a high amount of silver, silver is oxidized, and the ferric complex salt itself is reduced and ferrous complex ions are produced. It has been found that ferrous complex ions form ferrous complex ions and are present at high concentrations in the coating film of photographic light-sensitive materials during processing, leucoizing cyan dyes.

Poor color restoration due to leucoization of this cyan dye is caused by high sensitivity,
This was particularly noticeable in photographic materials with a high silver content type having a film thickness of 13 μm or more.

If the above ferrous complex ions accumulate in a bleach solution or bleach-fix solution at a high concentration, the ferrous complex ions in the photographic light-sensitive material coating produced by the bleaching reaction will significantly diffuse out of the coating. It is thought that this suppresses the production of leuco dye and increases the defective color recovery.

Generally, in order to oxidize the ferrous complex ions of the aminopolycarboxylic acid or aminopolyphosphonic acid and activate them to ferric complex ions, a method called aeration, in which air is blown into the treatment liquid to oxidize it, is well known. ing.

However, this method also oxidizes sulfite, which is a preservative, so it cannot be treated like color paper.
There is no danger if the fluid renewal rate is relatively high, but
When processing values are relatively small, such as color negatives, the oxidation of the liquid progresses too much, causing the preservative sulfite to oxidize, decomposing thiosulfate, precipitating sulfur (sulfide), and forming a precipitate, which is a serious problem. There is a risk of causing

Therefore, there is a strong demand for a method that does not cause poor color recovery even if ferrous complex ions are present to some extent.

It is also known that the above-mentioned poor color restoration can be improved by increasing the pH of the bleach solution or bleach-fix solution. Increasing the pH of the bleach-fix solution not only weakens the bleaching blade, but also makes it easier for ammonium thiosulfate and ferric ammonium salts to volatilize, causing odor to pollute the environment. It is not feasible to increase the pH of the bleach-fix solution.

Further, US Pat. No. 3,189,452 discloses a method in which, after bleaching and fixing, a red blood salt bleaching solution is used to oxidize a leuco dye and return it to a cyan dye.

However, the use of red blood salt has the above-mentioned pollution problems and has the disadvantage that it involves an extremely difficult red blood salt recovery operation for practical use.

In order to improve the above-mentioned drawbacks, the inventors of the present invention have developed a process that eliminates the above-mentioned problems such as pollution, has excellent desilvering performance, and has a high I)H alkaline bath treatment after the desilvering step. It has been found that poor color restoration can be improved.

However, a new problem has arisen in that treatment with such an alkaline bath increases the generation of cyansteine. The occurrence of cyanstein becomes more obvious when the amount of photosensitive material to be processed is small and the amount of preservative contained in the processing bath having fixing ability in the desilvering step is reduced. Therefore, there has been a desire for a method that can improve the recoloring properties without producing cyan stain as described above.

[Objective of the Invention] Therefore, the object of the present invention is to provide excellent processing stability even in the processing of color photographic light-sensitive materials, particularly silver halide color photographic light-sensitive materials of high sensitivity and high silver content type having a high film thickness, and in particular to improve processing stability of cyan dyes. It is an object of the present invention to provide a processing method that makes it difficult for leucoization to occur and also suppresses the generation of cyansteine.

[Structure of the Invention] The above object of the present invention is to carry out at least (a) a step of color development processing of an imagewise exposed silver halide color photographic light-sensitive material containing a compound represented by the following formula [C]; b) The following - Compound represented by [I] and [I
A step of treating 1112 silver using a treatment solution containing a ferric complex salt of at least one compound selected from the compounds represented by I], and (C) a step of treating with an alkaline bath having p)l of 8.0 or more. This has been achieved by a method for processing a silver halide color photographic material, which is characterized in that the processing is carried out in the processing steps including, in the above order.

General formula [C] (wherein, R1 bar CON R4Rs , -N HCO
R4, -NHCOORG, -NH8O2R6, -NH
CONR4R5 or -NH8O2NR4R5, R2 is a monovalent group, R3 is a substituent, X is a hydrogen atom or a group that leaves by reaction with an oxidized aromatic primary amine developer, l is O or 1 , m is an integer from 0 to 3, R4 and R5
each represents a hydrogen atom, an aromatic group, an aliphatic group, or a heterocyclic group, and R6 represents an aromatic group, an aliphatic group, or a heterocyclic group, and when m is 2 or 3, R3 is the same or different, respectively. including those that combine with each other to form a ring,
It also includes those in which R4 and Rs, R2 and Rs, and R2 and X combine to form a ring. However, when 1 is O, l is O
, R+ is -CONHRy, and R7 does not represent an aromatic group. ) General formula [I] General formula [1 [] [wherein L represents an alkylene group, a cycloalkylene group, a phenylene group, -La -0-La -0-La - or -LsZ-Ls-. Here 2 is L 12-1<
19 L 12- R19 and L1 to L+3 each represent an alkylene group. R11 to R21 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salts), or a phosphonic acid group (including its salts). However, R+t~R
At least two of +4 are carboxylic acids M (including salts thereof) or phosphonic acids M (including salts thereof), and at least one of R15 to R17 is a carboxylic acid group (including salts thereof) or a phosphonic acid group (including its salts). J In a more preferred embodiment, (1) the alkaline bath contains a chelating agent having a chelate stability constant (ffioaKMA) of 6 or more with iron ions; By containing a ferric carboxylic acid complex salt and (2) containing an oxidizing agent in the alkaline bath, the above object can be achieved more efficiently.

[Specific Structure of the Invention] The present invention provides a photosensitive material containing a cyan coupler represented by the general formula [C], which is prepared from a compound represented by the general formula [I] and the general formula [I[] as a bleaching agent. After desilvering using a ferric complex salt of at least one selected compound (hereinafter referred to as a ferric complex salt of the compound of the present invention), the pH is 8.0.
By treating with the above alkaline bath, the generation of cyanstein can be effectively prevented, and the first compound of the present invention, which is generated, adsorbed and accumulated in the gelatin coating of silver halide color photographic light-sensitive materials, can be effectively prevented. By desorbing iron complex ions and quickly diffusing them out of the gelatin coating system to create an alkaline atmosphere, the color development of the cyan dye is significantly accelerated and defective color restoration is improved.

In the processing method of the present invention, the desilvering treatment performed after the color development step may be any step that uses the ferric complex salt of the compound of the present invention as a bleaching agent.
Preferred typical examples of desilvering processes to which the present invention is applied are as follows.

[1] Bleach-fix [2] Bleach [3] Bleach-bleach-fix [4] Bleach-bleach-fix [5] Bleach-fix-bleach-fix, [61 Fix-bleach-bleach-fix Desilvering step above The ferric complex salt of the compound of the present invention is used as a bleaching agent in the bleaching and bleach-fixing processing baths, that is, the processing liquids having bleaching ability.

The compound of the present invention is at least one compound selected from a compound represented by the following general formula [I] and a compound represented by the general formula [''].

General Formula [I] General Formula [I] [wherein L represents an alkylene group, a cycloalkylene group, a phenylene group, -La -0-La -0-La - or -L9Z-Ls-. Here 2 is L 42- Rt
s L +2- R+s 1 to L13 each represent an alkylene group. R11 to R21 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salts), or a phosphonic acid group (including its salts). However, R11 to R+4
at least two of the R
At least one of +s to R17 is a carboxylic acid group (
(including its salts) or a phosphonic acid group (including its salts). ] The ferric complex salt of the compound of the present invention used in the treatment solution having bleaching ability of the present invention is a complex of ferric ion (Fe3 + ) and the compound of the present invention.

Typical specific examples of the compounds of the present invention are shown below.

A-1 Ethylenediaminetetraacetic acid disodium salt A-2 Ethylenediaminetetraacetic acid disodium salt A-3 Ethylenediaminetetraacetic acid diammonium salt -A-4 Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt A-5 Ethylenediaminetetraacetic acid tetrapotassium salt A-6 Ethylenediamine Tetraacetic acid tetrasodium salt A-7 Ethylenediaminetetraacetic acid trisodium salt A-8 Diethylenetriaminepentaacetic acid ammonium salt A-9 Diethylenetriaminepentaacetic acid pentasodium salt A-10 Ethylenediamine-N-(β-oxyethyl)
-N, N', N' -Triacetic acid A-11 ethylenediamine-N-(β-oxyethyl)-N, N', N'
-Triacetic acid trisodium salt A-12 ethylenediamine-N-(β-oxyethyl)
-N, N', N' - Triammonium triacetate salt A-13 Propylene diamine tetraacetic acid ammonium salt A-14 Propylene diamine tetraacetic acid disodium salt A-15 Nitrilotriacetic acid A-16 Nitrilotriacetic acid trisodium salt A-17 Cyclohexane Diaminetetraacetic acid A-18 Cyclohexanediaminetetraacetic acid disodium salt A-19 Iminodiacetic acid octa-20 dihydroxyethylglycine A-21 Ethyl ether diamine tetraacetic acid A-22 Glycol ether diamine tetraacetic acid A-23 Ethylenediamine tetrapropionic acid A-24
1,2-Diaminopropane tetraacetic acid ammonium salt A-25 1,2-diaminopropane tetraacetic acid sodium salt 8-26 Human O-ximinodiacetic acid ammonium salt A-27 Hydroxyiminodiacetic acid sodium salt A-28
Triethylenetetraminehexaacetic acid A-291,3-Diaminopropan-2-ol-tetraacetic acid A-30Phenylenediaminetetraacetic acid A-31Nitrilotripropionic acid A-32Ethylenediaminetetramethylenephosphonic acid A-33Diethylenetriaminepentamethylenephosphonic acid A -34 Cyclohexanediamine tetramethylene phosphonic acid A-35 Nitrilotrimethylene phosphonic acid A-36 Iminodimethylene phosphonic acid Among these compounds, aminopolycarboxylic acids are preferred, especially A-1 to A-3, A-8 ,A-13,A
-14, A-17 to A-19, A-22, and 8-24 to 8-27 are preferred.

The ferric complex salt of the compound of the present invention used in the present invention may be used in the form of a complex salt, or may be a ferric salt, such as ferric sulfate.
Ferric ion complex salts may be formed in solution using the compounds of the present invention with iron, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, and the like. When used in the form of a complex salt, one type of complex salt or two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and the compound of the present invention, one or more types of ferric salts may be used. Furthermore, one type or two or more types of compounds of the present invention may be used. Moreover, in any case, the compound of the present invention may be used in excess of the amount required to form the ferric ion complex.

Further, the bleaching solution containing the ferric ion complex described above may contain a complex salt of a metal ion other than iron, such as cobalt, copper, or nickel.

In the liquid having bleaching ability of the present invention, the ferric complex salt of the compound of the present invention is contained in an amount of 0.0% per y of the liquid having bleaching ability.
The amount is preferably 0.5 to 2 mol, more preferably 0.1 to 1.0 mol.
0 mol, particularly preferably in the range of 0.2 to -0.6 mol.

In the desilvering step of the present invention, when a bleaching solution is used, in addition to the ferric complex salt of the compound of the present invention as the bleaching agent, the bleaching solution includes boric acid, borax, metaboric acid, sodium hydroxide, potassium hydroxide, pH buffering agents consisting of various salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide,
It may optionally contain additives commonly used in bleaching solutions, such as halogen compounds such as sodium bromide, ammonium bromide, potassium iodide, sodium iodide, and ammonium iodide.

I)H of the bleaching solution of the present invention preferably ranges from 4.0 to 8.0, more preferably from 5.0 to 6.5.

When a bleach-fix solution is used in the desilvering step of the present invention, the bleach-fix solution contains, in addition to compounds that can be added to the bleach solution, silver halide fixing agents such as those used in ordinary fixing processes. compounds that react to form water-soluble complex salts,
For example, thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, high concentrations of bromides, iodides, etc. are used. . These fixing agents have a density of 5 g/2 or more, preferably 50 fl/l or more, more preferably 70 a/1. It can be used in an amount within the range that can be dissolved.

Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifoaming agents can be contained. Also, preservatives such as hydroxylamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, and polycarboxylic acids. , organic chelating agents such as dicarboxylic acids and aminopolycarboxylic acids, stabilizers such as nitro alcohols and nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, other additives, methanol, dimethylformamide, Organic solvents such as dimethyls and sulfoxide can be appropriately contained. .

The oH of the bleach-fix solution of the present invention is preferably in the range of 3.0 to 9.8, more preferably 5.6 to 8.5, particularly preferably 6.0 to 8.3.

When using a fixing solution in the desilvering step of the present invention, the fixing solution includes:
As a silver halide fixing agent, a fixing agent such as thiosulfate or thiocyanate mentioned in the above-mentioned bleach-fixing solution is contained.

In addition, as preservatives for the fixing agent, preservatives such as hydroxylamine, hydrazine, sulfites, isomeric bisulfites, binitrous acid adducts of aldehydes and ketone compounds, and various pHl1 buffers mentioned in the bleaching solution, It may contain known additives commonly used in fixers, such as halogen compounds.

The pH of the fixer is preferably in the range of 5.0 to 8.5, more preferably 6.0 to 8.0.

In the above desilvering process, the used bleach bath overflow solution flows out from the bleach bath as a result of adding the bleach replenisher to the bleach bath, and the used fixer bath flows out from the fixer bath as a result of adding the fixer replenisher to the fixing bath. A respective part or all of the overflow liquid can be introduced into the bleach-fixing bath. In this case, the overflow liquid from both the bleaching and fixing temperatures is effectively reused, the desilvering performance is not adversely affected, and the total amount of replenisher liquid can be reduced by 1, which is a preferred embodiment.

In the present invention, the desilvered silver halide color photographic light-sensitive material is treated at pH 8.0 or higher, preferably in an alkaline bath containing a buffer.

Here, when processing with an alkaline bath, it is of course necessary to perform continuous alkaline bath treatment after desilvering treatment, but also to wash with water, rinse, and roughen the powder before the alkaline bath treatment.
A stabilization treatment as an alternative to washing may be performed to extremely reduce the amount of water used for washing as described in No. 1, etc. Considering costs and the like, it is preferable to carry out continuous alkaline bath treatment after desilvering treatment.

The alkaline treatment solution of the present invention having a pi-18.0 or higher and containing a buffer (hereinafter simply referred to as the alkaline bath of the present invention) will be described below.

The buffer used in the alkaline bath of the present invention is “pi-1
Any compound can be used as long as it has a stable buffering effect in an aqueous solution of 8.0 or higher, but specific examples include sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, and ammonium bicarbonate. , IL acid, borax, meta I] sodium monoate, sodium phosphate, potassium phosphate, non-aMA such as monobasic sodium phosphate, amines such as ethanolamine, ethylenediamine, methylamine, trimethylamine, propylamine, hydroxyproline, leucine , amino acids such as glycine, alanine, aspartic acid, and γ-aminobutylacetic acid, and various organic compounds such as sulfosalicylic acid, piperazine, and guanidine, and these can be used alone or in combination.

As the buffering agent used in the present invention, sodium carbonate, potassium carbonate, bicarbonate, etc. are recommended in consideration of cost, the effect of improving the color recovery defect of the present invention, the pH maintenance effect during long-term continuous use, and the adverse effect on other photographic performance. potassium, boric acid,
Borax, sodium metaborate, sodium phosphate, potassium phosphate, monobasic sodium phosphate, sulfosalicylic acid, and the like are preferably used. - The usage of the above-mentioned buffer in the alkaline bath of the present invention varies greatly depending on the pH of the alkaline bath. Problems such as a small buffering effect may also occur, so this is determined by the conditions of the alkaline bath, but as a guideline, 0.00000000000000000000000000000000000000000000000000000000000000000000000000 per 12 alkaline bath.
It is preferably used in a range of 2 to 50q, more preferably 0.5 to 30g.

In the present invention, alkaline bath treatment can be carried out in part or in multiple baths, but preferably in one to two baths.

In addition, in the alkaline bath of the present invention, like other conventionally known photographic processing baths, a sufficient amount of replenisher may be supplied, but in consideration of pollution, etc., the amount of replenishment should be kept to a minimum. It is preferable to limit the

The amount of photographic processing solution brought into the alkaline bath from the prebath varies depending on the type of photosensitive material, the conveyance speed of the automatic processor, the conveyance method, the method of squeezing the surface of the photosensitive material, etc., but in the present invention, Based on the unit area of 25 tf/f ~ 150 tQ
/ f is preferable, and the replenishment amount at which the effect of the present invention is more remarkable during this period is 50 d/f to 3
．． 0! , /f, and the particularly effective replenishment amount is in the range of 100 iN/f to 950 tj2/f.

By containing a chelating agent having a chelate stability constant io (JKMA) of 6 or more with iron ions in the alkaline bath of the present invention, the effects of the present invention, specifically, the improvement of poor color recovery can be further improved. can be achieved effectively. It also has the effect of preventing hydroxide formation of soluble iron salts brought into the alkaline bath.

Here, the chelate stability constants are L and G.

5ill, en, A. E. Martell, “3 tabNityConstants of
Metal-ion Coulexes''.

The Chen+1cal 5ociety,
London (1964), S. Ch.
aberek, A, E, Martel! Author.

“Orclanic S 13QUelsterin
gA gentS means a constant generally known by Wiley (1959) and others.

In the present invention, examples of chelating agents having a chelate stability constant of 6 or more for iron ions include organic carboxylic acid chelating agents, organic aminopolycarboxylic acids, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhuman oxygen compounds. Can be mentioned. Note that the iron ion mentioned above refers to ferric ion (Fe
3'') and ferrous ion (Fe2'').

In the present invention, specific examples of compounds of chelating agents having a chelate stability constant of 6 or more with iron ions include the following compounds, but are not limited thereto. Namely, ethylenediaminediorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediamineniprobionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethyliminodiacetic acid. Acetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid, 1.1
-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-
1-phosphonopropane-1,2,3-tricarboxylic acid,
Catechol-3,5-disulfonic acid, sodium pyrophosphate, monohelium tetrapolyphosphate, and sodium hexametaphosphate are mentioned, and particularly preferred are diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, and diaminopropanoltetraacetic acid. ,
Ethylenediaminetetraacetic acid and salts thereof.

Good results can be obtained when the amount of the chelating agent used in the present invention is in the range of 0.01 to 50 (+, preferably 0.05 to 20) per 12 of the alkaline bath.

In the present invention, it is extremely preferable for the alkaline bath to contain a complex salt of the chelating agent and iron ions, that is, an iron complex salt, from the viewpoint of improving color restoration defects. Particularly preferred compounds include ferric sodium salt of ethylenediaminetetraacetic acid, ferric sodium salt of diethylenetriaminepentaacetic acid, ferric sodium salt of propylenediaminetetraacetic acid, and ferric sodium salt of 1゜2-diaminopropanetetraacetic acid. , the amount added is 0 per 12 alkaline baths.
．． It is 5 to 30 TJ, particularly preferably 2 to 15 C1.

In the present invention, the overflow liquid of the liquid having bleaching ability is poured into an alkaline liquid, and the ferric aminopolycarboxylic acid complex salt is present at a concentration of 1 x 10-3 mol or more per alkaline bath 111, thereby making it rough. Defects in color restoration can be effectively prevented.

Further, as an oxidizing agent in the alkaline bath of the present invention, for example, hydrogen peroxide, sodium percarbonate, sodium perborate, potassium persulfate, M ammonium sulfate, sodium chlorate, sodium hypochlorite, potassium bromate, ammonium bromate, By containing sodium bromate, rum, etc.
It is possible to effectively prevent poor recoloring. The oxidizing agent addition port is preferably o, o1g to 30g #! It is.

In the treatment method of the present invention, the above-mentioned alkaline bath treatment may be completed, and further treatment may be performed with water washing treatment or with a stabilizing treatment liquid that does not substantially use washing water.

In the present invention, the latter stabilization treatment that substantially does not use washing water is preferred as the treatment after the alkaline bath.

The stabilizer solution may basically consist of only water, but various compounds may also be added. Compounds that can preferably be used in the present invention include formalin, surfactants, ammonium salts, chelating agents, and metal salts. be.

A fungicide may be used in the alkaline bath or stabilizing solution of the present invention, if necessary. The antifungal agents used include hydroxybenzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds,
Carbamate compounds, morpholine compounds, quaternary phosphonium compounds, quaternary ammonium compounds, urea compounds, isoxazole compounds, propatoolamine compounds, sulfamide derivatives, amino acid compounds,
These are triazine compounds and benzotriazole compounds.

The color development process of the present invention can be carried out under usual conditions using a color developer used for ordinary silver halide color photographic materials.

In the processing method of the present invention, in addition to the steps such as color development, desilvering treatment, and alkaline bath treatment according to the present invention, various steps such as hardening, neutralization, black and white development, reversal, and small amount washing with water are performed as necessary. Auxiliary steps may be added.

The silver halide color photographic light-sensitive material used in the processing method of the present invention contains a cyan coupler represented by the general formula [CI].

Hereinafter, a cyan colorant according to the present invention will be explained.

In the general formula [C], the 6th base represented by R2-R7 includes those having a substituent.

R6 is an aliphatic group having 1 to 30 carbon atoms, or an aliphatic group having 6 to 30 carbon atoms;
An aromatic group having 30 carbon atoms and a heterocyclic group having 1 to 3 carbon atoms are preferable, and R+ and Rs are preferably hydrogen atoms, and those listed as preferable for R6 are preferable.

R2 is a hydrogen atom bonded to NH directly or via -NH-1-CO-1 or -8O2-, a C1-C30 fatty ta! ! , an aromatic group having 6 to 30 carbon atoms,
C1-30 heterocyclic group, -CO2Rho, -80
2Rho or -8O20R1G (R8, Rs and Rh
o is the same as defined in R, R5 and R6, respectively, and R8 and R9 may be combined to form a heterocycle. ) is preferred.

R7 is preferably an aromatic group having 6 to 30 carbon atoms;
Typical examples of substituent 7 include halogen atom, hydroxy group, amino group, carboxyl group, sulfonic acid group, cyano group, aromatic group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group,
Aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imido group, aliphatic group, aliphatic oxycarbonyl group, etc. Can be done.

When substituted with a plurality of substituents, the plurality of substituents may be bonded to each other to form a ring, such as a dioxymethylene group.

Typical examples of R3 include halogen atom, hydroxy group, amino group, carboxyl group, sulfonic acid group, cyano group, aromatic group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group,
Acyl group, acyloxy/cy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide group, etc. can be mentioned, and this R
The number of carbon atoms contained in 3 is preferably 0 to 30. An example of cyclic R3 when 1-2 is a dioxymethylene group.

When l is 1, R1 is particularly preferably -CONRR5, ■ is preferably 0, and R2 is -CO directly bonded to NH.
Ra, GOORlo, -8O2Rho, -CON
Ra Rs , -8O2NRa Rs are particularly preferred;
Even more preferred is COOR1o which binds directly to NH.
, -CORa, -802Rlo, -COOR
+o is most preferred.

Also included in the present invention are those that form dimers or more multimers via R1-R3 and X.

- A specific example of the coupler represented by the coin [0] is published in Japanese Unexamined Patent Publication No. 6
No. 0-237448, No. 61-153640, No. 61
-145557, 62-85242, 48-1
No. 5529, No. 50-117422, No. 52-18
No. 315, No. 52-90932, No. 53-52423
No. 54-48237, No. 54-66129, No. 55-32071, No. 55-65957, No. 55-
No. 105226, No. 56-1938, No. 56-126
No. 43, No. 56-27147, No. 56-126832
No. 58-9534Ei and U.S. Patent No. 3.488
．． No. 193, etc., and can be synthesized by the methods described therein.

To add the cyan coupler of the present invention into a light-sensitive material,
Depending on the physical properties of the coupler (for example, solubility), oil-in-water emulsion dispersion using a water-insoluble high-boiling organic solvent, alkaline dispersion using an alkaline solution, latex dispersion, or solid dispersion adding directly as a fine solid. Various methods can be used, such as the method.

The amount of the above coupler added is usually per mole of silver halide.
1. OX 10-3 mol to 1.0 mol, preferably -
The range is from 5,0X1Q-' moles to 8.0XIO-' moles.

Next, typical examples of the coupler represented by the general formula [0] will be shown, but the present invention is not limited thereto.

m2 m4 m5 m6 C-12 し＋　o　Plz　＋　U　し（J　　t’1m20 285υC (JNH C,,H2゜ C, 2H□ C-29 ／−１−−−−−＼ Yam CH, CH, 5CH2CH, CO, H CH, CH2NH30, CH.

C-38 L'θ CH2CH25CHCI2H2S CO,H
-56 C-57 C12H25 C3゜H2゜OOH OOH 0CH2CONHCI2Hxs OOH OOH 0OH CH.

CO□H The silver halide color photographic material containing the cyan coupler according to the present invention, which is applied to the processing method of the present invention, is basically not limited in type, but it is particularly effective for use in the present invention. One is a high-sensitivity photographic light-sensitive material having silver halide grains containing silver iodide in an amount of 0.5 mol % or more, preferably 3 to 10 mol %, in at least one of the silver halide emulsion layers. In addition, the total dry film thickness of all the photographic constituent layers on the side having the silver halide emulsion layer on the support is 13
It is a photosensitive material having a diameter of 1 μm or more, preferably 15 μm to 28 μm, more preferably 17 μm to 24 μm, and furthermore, the amount of silver coated on the support is 20111 (1/100 Ct'
Above, preferably 30111g/100Ct? ~80
m (1/100C,!, more preferably 40Ig/1
It is a photographic material with a high silver content of 00 Cf to 70 mg/100 cf.

The silver halide emulsion of the silver halide color photographic light-sensitive material applicable to the present invention can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

In addition to the cyan coupler according to the present invention, any conventionally used magenta coupler and yellow coupler can be used in the emulsion layer of the full-color photographic light-sensitive material, and in particular, a magenta coupler represented by the following general formula [M-I] is used. is preferable in the sense that it improves the color development of the magenta dye.

General formula [M-I] (In the formula, 2. represents a group of non-metallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by the group may have a substituent.

Xs represents a hydrogen atom or a vine group that is released upon reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent. ) general formula [M-I
], there are no particular restrictions on the substituent represented by R, but
Typically, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio,
Examples include multiple groups such as alkenyl and cycloalkyl,
In addition, halogen atoms, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyl oxide, sulfamoylamino, alkoxycarbonylaminolkoxycarbonyl, aryloxycarbonyl, polycyclic thio, and spiro Also included are compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

X. Examples of groups that can be separated by reaction with oxidized color developing agents include halogen atoms (chlorine atoms, bromine atoms, fluorine atoms, etc.), alkoxy, aryloxy,
Heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxythi A, arylthio, polycyclic thi A, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing 1i ring bonded by N atom, Alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, (R' has the same meaning as R, 2' has the same meaning as z0, R2 and R3 each represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group) ), preferably a halogen atom, particularly a chlorine atom.

Examples of the nitrogen-containing heterocycle formed by Ze or 2' include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned.

What is represented by the general formula [M-IF] is more specifically represented by, for example, the following - coins [M-n] to [M-Vl].

[M-1[] [M-1[[] [M-IV] [M-Vl [M-VI] ~-to-Nl-1 General formula [M-■] Said - coin [M-[1~ R+'~R in [M-■]
a' and X have the same meanings as R and xo above.

Among the magenta couplers represented by the above-mentioned formulas [M-It] to [M-■], particularly preferred ones are of the general formula [M-I!
] is a magenta coupler.

- The substituent that the ring formed by zo in M-II may have, and - The money CM-II] ~ [M
-Vl ] (as R2' to Ra', the following -
It is preferable to use coins expressed as [M-■].

-Throwing money [M-■] -R'' -802-R5 In the formula, R4 represents an alkylene group, and R5 represents an alkyl group, a cycloalkyl group, or an aryl group.

The alkylene group represented by R4 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and it does not matter whether the straight chain has one branch or not.

The cycloalkyl group represented by R5 is 5 to . Six-membered ones are preferred.

In addition, when used for positive image formation, the substituent R on the heterocycle
The most preferable one for R1′ and R1′ is the following:
−4X ].

- Throwing money [M-IX] Rs' In the formula, Rs', Rho' and R11' each have the same meaning as R above.

Also, two of the above Rs', Rho' and R11', for example R9' and R1o', are bonded to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene, heterocycle).
Furthermore, R11' may be bonded to the group ring to form a bridged hydrocarbon compound residue.

Among the general formulas [M-IX], preferred are (i
) When at least two of Rs'-Ra1' are alkyl groups, (ii) one of Rs' to R11'
For example, R++ is a hydrogen atom, and the other two R, l
and Rho' combine to form a cycloalkyl with the root carbon atom.

Furthermore, it is preferable among (i) that two of R91 to R11' are alkyl groups and the other one is a hydrogen atom or an alkyl group.

In addition, when used for negative image formation, the substituent R on the heterocycle
And R11 is most preferably represented by the following general formula [M-
X ].

General formula [M-X] R12'-〇H2- In the formula, R12' has the same meaning as R above.

Preferred as R12' is a hydrogen atom or an alkyl group.

Typical specific examples of the magenta coupler represented by the general formula [M-11] according to the present invention are shown below.

In addition to the above representative examples of the magenta coupler represented by the general formula [M-I] according to the present invention, specific examples of the magenta coupler according to the present invention are disclosed in Japanese Patent Application No. 61-9791.
Among the compounds described on pages 66 to 122 of the specification, N011 to 4.6.8 to 17.19 to 24.2
6~43.45~59°61~104. 106-12
1. 123-162. Compounds represented by 164 to 223 can be mentioned. Furthermore, the patent application No. 61-288
No. 370 Mei 1l 11 pages 20 to 32 and patent application No. 1983
Compounds described in No. 65314, Mei II 1, pages 16 to 30 can also be mentioned.

In addition, the coupler is described in the Journal of the Chemical
Society (Journal of the Chem)
ical 3ociety), perki
n) 1 (1977), 2047-2052, U.S. Patent No. 3.725.067, JP-A-59-99437
No. 58-42045, No. 59-162548,
No. 59-171956, No. 60-33552, No. 6
No. 0-43659, No. 60-172982 and No. 60
It can be synthesized by referring to No.-190779 and the like.

The couplers of the invention are typically 1x1 per mole of silver halide.
o-a mole-1 mole, preferably lXl0-2 mole to 8
It can be used in the range of X1G'' moles.

The above couplers can also be used in combination with other types of magenta couplers.

By containing the magenta coupler represented by the above-mentioned -Isen [M-I], magenta stain and processing fluctuations, especially cyan recolorability, are surprisingly improved.
This fact is noteworthy as well as the effect of the present invention.

Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, Compounds that release photographically useful fragments such as fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

- A matting agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retardant, and a bleach accelerator can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example-1 From the support side, a black colloidal silver antihalation layer, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer were formed, and the blue-sensitive silver halide emulsion layer was A monodisperse high-sensitivity silver halide emulsion layer was disposed on the outermost side of the silver emulsion layer to prepare sample N011. However, the amount of coated silver was 60 mg/100C12, and the dry film thickness was 25 μm.

Layer 1: 0.8 g of black colloidal silver, which is highly absorbent to light in the wavelength range of 400 to 700 rv, prepared by reducing silver nitrate with hydroquinone, is dispersed in 3 g of gelatin to make a dispersion, and an antihalation layer is formed. Painted.

! 12...Middle layer made of gelatin.

Layer 3: 1.5 g of low-sensitivity red-sensitive silver iodobromide emulsion (A
gI nmol%), 1.8 g gelatin and 0.90
g of 1-hydroxy-4-(β-methoxyethylaminocarbonylmethoxy)-N-[δ-(2,4-di-t-
amylphenoxy)butyl]-2-naphthamide (hereinafter referred to as cyan coupler (C-0)) and 0.032 g
1=Hydroxy-4-[4-(1-humanOxy8-
acetamido-3,6-disulfo-2-naphthylazo)
phenoxy]-N-[δ-(2,4-di-amylphenoxy)butyl]-2-naphthamide disodium (hereinafter referred to as colored cyan coupler (CC-1)) was dissolved in 0, 4+3 trichloride. A low-sensitivity red-sensitive silver halide emulsion layer containing dilphosphate (hereinafter referred to as TCP).

Layer 4...1.3g of highly sensitive red-sensitive silver iodobromide emulsion (A
! J! 6 mol%), 1.3 g gelatin and 0.28
0.17Q in which g of cyan coupler (C-0) and 0.0200 of colored cyan coupler (CG-1) were dissolved.
A highly sensitive red-sensitive silver halide emulsion layer containing TCP.

Layer 5: 0.04 (l) of dibutyl phthalate (hereinafter referred to as "antifouling agent (HQ-1)") in which 0.08 g of 2,5-di-octylhydroquinone (hereinafter referred to as antifouling agent (HQ-1)) was dissolved.
DBP) and 1.2 g of gelatin.

Layer 6: 1.6 g of low-sensitivity green-sensitive silver iodobromide emulsion (A
gI; 6 mol%), 1.7 g of gelatin and 0.32
g of 1-(2,4,6-dolichlorophenyl)-3-
[3-(2,4-di-t-amylphenoxyacetamide)benzenamide]-5-pyrazolone (hereinafter referred to as magenta coupler (M-1)), 0.20Q of 4.4-
methylenebis-11-(2,4,6-dolychlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamide)benzenamide]-5-pyrazolone (hereinafter referred to as magenta coupler (M- 2)) and 0.06
61;l of 1-(2,4,6-dolichlorophenyl)
-4-(1-naphthylazo)-3-(2-chloro-5-
A low-sensitivity green-sensitive halogen containing 0.3 g of TCP dissolved in three types of couplers: octadecenyl succinimide anilino)-5-pyrazolone (hereinafter referred to as colored magenta coupler (CM-1)). Silver emulsion layer.

Layer 7: 1.5 g of high-sensitivity green-sensitive silver iodobromide emulsion <I
I: 8 mol%), 1.9 g of gelatin and 0.10 (
0.12 (l) of magenta coupler (M-1), 0.098 iJ of magenta coupler (M-2) and 0.049Q of colored magenta coupler (CM-1) were dissolved.
A highly sensitive green-sensitive silver halide emulsion layer containing TCP.

118...0.2g yellow colloidal silver, 0.2! DB of 0,1113 in which J's anti-fouling agent (HQ-1) was dissolved
Yellow filter layer containing P and 2.1 g of gelatin.

Layer 9...0.95! II low-speed blue-sensitive silver iodobromide emulsion (Agf nmol%), 1.9 g of gelatin and 1
．． 84 g of α-[4-(1-benzyl-2-]nyl-3,5-dioxo1,24-doriazolidinyl)]
−]α-pivaloyru2-chloro5 [7-(2,4
A low-sensitivity blue-sensitive silver halide emulsion layer containing 0.93 g of DBP in which -di-t-amylphenoxy)butanamide 1 acetanilide (hereinafter referred to as yellow coupler (Y-1)) was dissolved.

Layer 10...1.2g of highly sensitive monodisperse blue-sensitive silver iodobromide emulsion (AgI: 6 mol%), 2.0g of gelatin and 0.46g of yellow coupler (Y-1) were dissolved.
, a highly sensitive blue-sensitive silver halide emulsion layer containing DBP of 23Q.

Layer 11: Second protective layer made of gelatin.

1912...first protective layer containing 2.3 g of gelatin.

Samples Nos. 32 to 15 were prepared in the same manner as in the above sample No. 11, except that the cyan couplers (C-0) in layers 3 and 4 were replaced with the exemplified cyan couplers of the present invention as shown in Table 2. did.

These samples were cut into pieces, subjected to model exposure according to a conventional method, and processed using a piece processing device according to the following steps (hereinafter referred to as half-ring processing).

Processing process Processing temperature ("C) Number of tanks Processing time 1, color development 37.8 1 tank 3 minutes 15 seconds 2, bleach-fixing 37.8 1 tank 3 minutes 30 seconds (However, I and H of the bleach-fix solution are as follows. 3. Alkaline bath 30-34 2 tanks 3 minutes 30 seconds (However, the pH of the alkaline bath was as shown in Table 1 below.)

) 4. Stability 30-34 1 tank 2 minutes 10 seconds 5. Dry The following were used as the dry color developing solution, bleach-fix solution, alkaline bath solution, and stabilizing solution.

- [Color developing solution] [Bleach-fixing solution] U ethylenediaminetetraacetic acid Further, silver powder was added and the ferric diammonium salt of ethylenediaminetetraacetate was reduced to produce 500% of the ferrous diammonium salt of ethylenediaminetetraacetate. The DH was adjusted as shown in Table-1.

[Alkaline bath solution] [Stabilizing solution] Table 1 A photosensitive material sample was processed according to the above, and residual silver Il (I1g/df) in the highest concentration part of the processed sample was measured using fluorescent X
Measured by line method. Furthermore, the cyan dye concentration was measured using a Sakura photoelectric densitometer PDA-65 (manufactured by Konishiroku Photo Industry ■), and using this value, the same sample was 3%
The color recovery rate was calculated by setting the cyan dye concentration of the dye treated with a blushing salt solution for 3 minutes at room temperature to 100. In addition, the cyan dye density (cyan stain) of the unexposed area is
A-65 was measured in the same manner.

The results are summarized in Table-2.

Table 2 Table 2 (Continued) As is clear from the results in Table 2, after desilvering with a bleach-fix solution, 1) those treated with an alkaline bath of H8.0 or higher have less desilvering and cyan dye. Color restoration defects have been significantly improved. However, in an experiment in which sample No. 091 was processed without using the coupler of the present invention as a cyan coupler, cyan stain occurred. On the other hand, in an experiment in which samples Nos. 32 to 18 containing the cyan coupler of the present invention were desilvered and then treated in an alkaline bath with a pH of 8.0 or more, the generation of cyansteine was well suppressed, and the desilvering property was excellent and the recovery was good. Color defects have also been significantly improved.

Example-2 The following alkaline bath was prepared.

[Alkaline bath solution] Example-1 as a bleach-fix solution using the above alkaline bath
1) Experiments and evaluations similar to those in Example-1 were carried out, except that H6,5 and photosensitive material samples Nos. 1 and 2 of Example-1 were used.

Furthermore, regarding the alkaline bath, 5
After being stored at 0° C. for 5 days and 10 days, each sample was treated in the same manner as above using each storage alkaline bath, and the deterioration of the storage over time in the alkaline bath was observed.

The results are also shown in Table 3.

As is clear from the results in Table 3, in Experiments 2-2 to 2-5, in which samples containing cyan couplers other than those of the present invention were treated with monoalkaline baths with a pH of 8.0 or higher, poor color restoration was improved even after aging. Although it is effective, it also causes a large amount of cyanstein. Furthermore, in Experiment 2-1, the color recovery failure was also large. On the other hand, in experiments 2-7 to 2-18 in which samples containing the cyan coupler of the present invention were treated with an alkaline bath of p) -18.0 or higher,
Even after aging, the improvement effect on poor color restoration is significant and cyan stain is well suppressed. In addition, when the alkaline bath does not contain an 8% agent as in Experiment 2-19, the effect of improving poor color recovery and suppressing cyansteine is satisfactory immediately after preparing the alkaline bath, but as time passes, the rate of color recovery becomes particularly insufficient. It can be seen that a stable photographic image cannot be obtained.

Example-3 Processing steps in Example-1, namely 11 color development, 2.
Bleach fixing, 3. Alkaline bath, 4. An experiment was conducted by replacing each stable treatment step with a treatment step such as Cloth-4 below.

Table 4-2 Among the processing solutions used in the above processing steps, the bleach-fix solution used in Example-1 with p)l of 6.5 was used, and the alkaline bath used the same with p)l of 110.0. . Furthermore, the following components other than the bleaching solution and fixing solution were the same as those in Example-1.

[Bleach Solution 1 In the same manner as in Example 1, silver powder was added to reduce the ferric diammonium salt of ethylenediaminetetraacetate, so that the amount of the ferrous diammonium salt of ethylenediaminetetraacetate was 50 g.

[Fixer] An experiment similar to Example 1 was conducted except for the above processing steps,
The recoloring rate, desilvering property, and cyanstein were examined. In addition,
The photosensitive material samples used were N011 and N002 of Example-1.
It is. The results are shown in Table-5.

As is clear from the results in Table 5, even if the desilvering treatment was varied, poor color recovery was significantly improved by applying the alkaline bath treatment of the present invention. However, in experiments using photosensitive material samples containing cyan couplers other than those of the present invention, cyan stain was large. On the other hand, it can be seen that the sample containing the cyan coupler of the present invention maintains the effect of improving poor color restoration and suppresses cyan stain well.

Example 4 In Example 1 above, photosensitive material sample No. 12 was used, the pH of the bleach-fixing solution was 6.5, the pH of the alkaline bath was 10,
Furthermore, in place of the ferric diammonium salt of ethylenediaminetetraacetic acid as the aminopolycarboxylic acid in the bleach-fix solution, the aminopolycarboxylic acid ferric acid shown in the following Clothing-6 was added.
An experiment was conducted in the same manner as in Example 1, except that the iron complex salt was used at the concentration shown in Table 6. The results are also shown in Table 6.

Table 6 As is clear from the results in Table 6, it can be seen that the effects of the present invention can be obtained even if the type and concentration of the bleach used in the bleach-fix solution are changed.

Example 5 An experiment was carried out in the same manner as in Experiment No. 4-1 of Example 4, except that 10 (]) of the additives shown in Table 7 below were added to the alkaline bath 11.

θOOOO■@θ[Phase]■C1UO◎[Phase] As is clear from the results in Table 7, in the treatment method of the present invention, a chelating agent with a stability constant of 6 or more with iron is added to the alkaline bath. The improvement effect of poor color recovery according to the present invention is even more remarkable when the ferric aminopolycarboxylic acid complex salt is contained at a certain concentration or more, and when an oxidizing agent is further contained. I understand that.

Example-6 In Example-1, using photosensitive material sample No. 2,
The experiment was conducted in the same manner as Experiment No. 31-4, except that the film thickness of the photosensitive material (the film thickness was changed only for Gelatin Gake) and the amount of coated silver was changed and the photosensitive materials shown in Table 8 below were used. . However, for comparison, an experiment was conducted in which no alkaline bath was used. The results are also shown in Table-8.

Table 8 As is clear from the results in Table 8, the processing method of the present invention is not significantly affected by the film thickness of the photosensitive material or the coated silver ω, and has a good effect of improving color restoration defects and cyan staining. The obtained film thickness is 13 μm or more. (film thickness 13μ
If the thickness is less than I, the restoration defect is small, but the magenta tin is large.) When the thickness of III is 16 μm or more, a particularly large improvement result is obtained, and it can be seen that the larger the amount of coated silver, the greater the improvement effect.

Example-7 In Example-1, the photosensitive material N002 was used, the magenta coupler shown in Table-9 (equivalent molar to M-2) was used instead of M-2 as the magenta coupler, and processing N0.1-3 was used.
Processed with. After the treatment, the transmission density of cyan and magenta in the unexposed area was evaluated in the same manner as in Example-1. The results are shown in Table-9.

However, in Table 9, only magenta is listed.

Table-9 From Table-9, magenta couplers are exemplified by compound (1), (
3), (7), or (14) improves magentastin in the unexposed area.

We also examined the cyan color restoration rate and the cyan stain in the unexposed area, and found that the use of the magenta coupler surprisingly improved the color restoration rate by about 3 to 5%.

[Effect of the invention J As explained in detail above, the treatment method of the present invention provides
Improves processing stability in the processing of color photographic materials, especially silver halide color photographic materials with high sensitivity and high silver m-type film thickness, and particularly suppresses leuco formation of cyan dyes and the occurrence of cyan stain. can do.

Patent applicant Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Scope of Claims] At least (a) color development processing of an imagewise exposed silver halide color photographic light-sensitive material containing a compound represented by the following general formula [C]; (b) a step of color development processing;
(c) a step of desilvering using a treatment solution containing a ferric complex salt of at least one compound selected from the compound represented by [I] and the compound represented by [II], and (c) pH 8
．． 1. A method for processing a silver halide color photographic light-sensitive material, characterized in that the processing is carried out in the steps described above in the above order, including the step of processing in an alkali bath of 0 or more. General formula [C] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is -CONR_4R_5, -NHCOR
_4-NHCOOR_6, -NHSO_2R_6, -N
HCONR_4R_5 or -NHSO_2NR_4R_
5, R_2 is a monovalent group, R_3 is a substituent, X is a hydrogen atom or a group that leaves by reaction with an oxidized aromatic primary amine developer, l is 0 or 1, m is An integer from 0 to 3, R_4 and R_5 are each a hydrogen atom, an aromatic group,
an aliphatic group or a heterocyclic group, R_6 represents an aromatic group, an aliphatic group, or a heterocyclic group, and when m is 2 or 3, R_
3 are the same, different, and combine with each other to form a ring, and also include R_4, R_5, R_2
and R_3, and those in which R_2 and X combine to form a ring are also included. However, when l is O, m is O, and R_1 is -CONH
R_7, and R_7 represents an aromatic group. ) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, L is an alkylene group, cycloalkylene group, phenylene group, -L_8- Represents O-L_8-O-L_8- or -L_9-Z-L_9-. Here, Z represents ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. L_1 to L_1_3 each represent an alkylene group. R
_1_1 to R_2_1 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt), or a phosphonic acid group (including its salt). However, at least two of R_1_1 to R_1_4 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and R_1
At least one of _5 to R_1_7 is a carboxylic acid group (including its salt) or a phosphonic acid group (including its salt). ]