JPH06103382B2 - Method for forming color photographic image - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a method for forming a color photographic image using a silver halide color photographic light-sensitive material (hereinafter referred to as a light-sensitive material), and more specifically, after omitting a water washing treatment step, for long-term storage after the treatment, The present invention relates to a method for forming a color photographic image capable of forming a dye image having excellent storage stability.

[Prior art]

For the purpose of speeding up, a light-sensitive material in recent years is subjected to a color developing process, a bleach-fixing process and a washing process after image exposure. And in such a treatment process, in recent years depletion of water resources,
Increasing costs for water washing due to higher crude oil prices are becoming an increasingly serious problem. Therefore, as a method of omitting the washing treatment step or reducing the amount of washing water extremely, a multistage countercurrent stabilization treatment technique as described in JP-A-57-8543 and JP-A-58-1
A treatment technique using a water-washing alternative stabilizing solution containing a bismuth complex salt as described in Japanese Patent No. 34636 has been proposed. These technologies are technologies for reducing pollution by reducing the amount of replenishment of the stabilizing solution for washing and reducing pollution, but the photographic images obtained by applying these technologies are extremely insufficient in storage stability over time. Techniques for improving such problems have been proposed, and techniques for preventing leuco formation of cyan dyes by performing a final treatment in the presence of a soluble iron complex salt as a technique for improving fading of cyan dye images under high temperature and high humidity. JP 58-148
Known by No. 34. However, most of the actual fading of photographic images is due to light and aging, and the development of technology to prevent fading due to the effects of both light and aging is naturally desired. There is a demand for technology to prevent this.

[Object of the Invention]

Therefore, it is an object of the present invention to provide a method for processing a light-sensitive material which does not substantially use washing water and has a low energy cost and a low pollution load. Another object of the present invention is to provide a method capable of forming a stable color photographic image during long-term storage without substantially using washing water.

[Constitution of the invention]

 An object of the present invention is to represent cyan cyan represented by the following general formula [I].
Development of silver halide color photographic light-sensitive material containing puller
Organics with a free acid molecular weight of less than 280 immediately after color development
Processing with a bleach-fix solution containing ferric acid complex salt, followed by
The following general formulas [V] and [V
I) or [VII] Chelating agent containing a chelating agent
Of color photographic images, characterized by being processed with a replacement stabilizer
This is achieved by the forming method. General formula [I]Where R and R₁One is a hydrogen atom and the other is less
Both are linear or branched alkyl groups having 2 to 12 carbon atoms,
X is a hydrogen atom or an acid of an aromatic primary amine color developing agent
Represents a group capable of leaving by a coupling reaction with a compound, R₂
Represents a ballast group. General formula [V] A-COOM General formula [VI] B-PO₃M₂ General formula (VII)In the formula, A and B each represent a monovalent group or atom, and D
Represents an aromatic ring or a heterocyclic ring which may have a substituent, and M
Represents a hydrogen atom or an alkali metal atom. Hereinafter, the present invention will be described in detail. Conventionally, as a bleaching agent used in a bleach-fixing solution, an organic acid ferric complex is used.
Salts are known and thiosulfate is used as a fixing agent.
Ordinary bleaching that uses sulfite as a preservative
In the fixer, ethylenediamine tetrachloride was used as the ferric organic acid complex salt.
Ferric acetate is used. Ethylenediaminetetraacetic acid
The reason for using ferric iron is the desilvering property of the bleach-fixing solution, the color recovery property, and
This is because it is preferable in terms of liquid storage stability. Therefore, use a large amount of water following the bleach-fix processing step.
Washing process used for washing with a small amount of aqueous solution
Ethylenediamine is used instead of the liquid treatment process.
Treatment with a bleach-fixing solution using ferric tetraacetate as a bleaching agent
It is used as the next bath in the physical process. And like this
In such a system, the cyan dye as described above and
There is a problem that the color fading is bad and not enough
It As a result of earnest research on this problem, the present inventor was surprised.
What is remarkable is that the cyan coupler represented by the general formula [I]
And a bleach-fixing solution bleaching agent.
And use ferric salts of organic acids with a free acid molecular weight of less than 280
And further represented by the general formula [V], [VI] or [VII]
When treated with an alternative stabilizing solution containing water containing a chelating agent
The present invention was found to solve the above technical problems and
It is a thing. Further, the free acid of the ferric organic acid salt is represented by the general formula [IV].
The effect of the present invention is particularly remarkable when the compound is
It has been found that and are extremely preferable. The cyan dye-forming coupler according to the present invention has the general formula
It can be represented by [I].
Further description will be made. In the present invention, R in the general formula [I] is₁, Charcoal represented by R
A linear or branched alkyl group having a prime number of 2 to 12 is, for example, an ethyl group.
Group, propyl group, and butyl group. In the general formula [I], R₂The ballast group represented by
The coupler is substantially expanded from the layer to which the puller is applied to other layers.
Bulky enough to keep the coupler from
It is an organic group having the size and shape given to the child.
It A typical ballast group has a total carbon number of 8 to 32
Examples thereof include an alkyl group and an aryl group, and preferably
The total carbon number is 13-28. These alkyl groups and aryls
As the substituent of the group, for example, an alkyl group, an aryl group,
Alkoxy group, allyloxy group, carboxy group, acyl
Group, ester group, hydroxy group, cyano group, nitro group,
Carbamoyl group, carbonamido group, alkylthio group,
Arylthio group, sulfonyl group, sulfonamide group, sulfur
Rufamoyl group, halogen, alkyl group
As the substituent of, the aryl group excluding the alkyl group is
The substituents mentioned above can be mentioned. Preferred as the ballast group is represented by the following general formula.
It is something.R₁₂Represents an alkyl group having 1 to 12 carbon atoms, Ar is phenyl
Represents an aryl group such as a group, and this aryl group has a substituent.
You may have. As the substituent, an alkyl group, a hydro group
Xy group, halogen atom, alkylsulfonamide group, etc.
However, the most preferable one is a component such as t-butyl group.
Various alkyl groups are mentioned. Of the color developing agent defined by X in the general formula [I]
A group that can be split off upon coupling with an oxidant is well known to those skilled in the art.
As is known, it is common to determine the number of equivalents of a coupler.
In addition, it affects the coupling reactivity. As a typical example,
Chlorine, halogen represented by fluorine, aryloxy
Group, substituted or unsubstituted alkoxy group, acyloxy group,
Sulfonamide group, arylthio group, heteroylthio group
Group, heteroyloxy group, sulfonyloxy group, carba
A moyloxy group etc. are mentioned. As a more specific example
JP-A-50-10135, 50-120334, 50-130414
No. 54, No. 54-48237, No. 51-146828, No. 54-14736, No. 4
7-37425, 50-123341, 58-95346, Sho 48-3
6894, U.S. Pat.Nos. 3,476,563, 3,737,316 and 3,
The groups described in each publication of 227,551 are mentioned. Next, exemplified compounds of the cyan coupler represented by the general formula [I]
Examples include, but are not limited to: The method for synthesizing the exemplified compound of the present invention is shown below, but other
The exemplified compounds can also be synthesized by the same method. Synthesis Example of Exemplified Compound C-5 [(1) -a] 2-Nitro-4,6-dichloro-5-e
Synthesis of tylphenol 33 g of 2-nitro-5-ethylphenol, 0.6 g of iodine and
Dissolve 1.5 g of ferric chloride in 150 ml of glacial acetic acid. 40 ℃ to this
Then, 75 ml of sulfuryl chloride is added dropwise over 3 hours. Dripping
Precipitate formed on the way was completed with the addition of sulfuryl chloride.
After that, by heating under reflux, the reaction is dissolved. Heating reflux
Takes about 2 hours. Crystals formed by pouring the reaction solution into water
Is purified by recrystallization with methanol. (1) -a confirmation
Was performed by nuclear magnetic resonance spectrum and elemental analysis. [(1) -b] 2-Nitro-4,6-dichloro-5-d
Synthesis of tylphenol 21.2 g of the compound [(1) -a] was dissolved in 300 ml of alcohol.
Dissolve it, add a catalytic amount of Raney nickel to it, and
Hydrogen was passed through until there was no more hydrogen absorption. After the reaction
The ice ax was removed and the alcohol was distilled off under reduced pressure. Residue
[(1) -b] of the above is subjected to the next acylation without purification.
It was. [(1) -c] 2 [(2,4-di-tert-acylpheno
Xy) acetamide] -4,6-dichloro-5-ethylphenyl
Synthesis of the enol [1 (1) -b] The crude amino compound 18.5 g obtained in [500 ml]
Dissolved in a mixed solution of glacial acetic acid and 16.7 g of sodium acetate,
To this was added 2,4-di-tert-aminophenoxyacetic acid chloride 2
Add acetic acid solution prepared by dissolving 8.0 g in 50 ml of acetic acid at room temperature.
It Add dropwise over 30 minutes, stir for another 30 minutes, and then place the reaction mixture in ice water.
inject. The precipitate formed is collected by filtration, dried, and washed with acetonitrile.
The desired product can be obtained by recrystallizing twice. Definite target
It was confirmed by elemental analysis and nuclear magnetic resonance spectrum.The cyan coupler according to the present invention represented by the general formula [I] is
When it is contained in the silver halide emulsion layer, it is usually a halogen
About 0.005 to 2 mol, preferably 0.01
It is used in the range of 1 mol. The light-sensitive material used in the method of the present invention is halogenated on a support.
One coated with a silver emulsion layer and a non-photosensitive layer (non-emulsion layer)
And silver halide emulsions include silver chloride, silver bromide,
Such as silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide
Any silver halide may be used. This
These emulsion layers and non-light sensitive layers are known in the photographic industry.
It is possible to include all couplers and additives.
, For example, yellow dye-forming couplers, magenta dyes
Forming coupler, cyan dye forming coupler, stabilizer, sensitizing
Dyes, gold compounds, high boiling organic solvents, antifoggants, dyes
Image fading prevention agent, color stain prevention agent, fluorescent whitening agent, antistatic
Agents, Hardeners, Surfactants, Plasticizers, Wetting Agents and UV
An absorber or the like can be appropriately contained. The light-sensitive material used in the method of the present invention may be the above-mentioned
Emulsion layers containing various photographic additives such as
Corona discharge treatment, flame treatment of each constituent layer such as photosensitive layer
Or on a support that has been subjected to UV irradiation, or undercoat
Layer by coating on the support through the intermediate layer
Is built. Examples of supports that can be advantageously used include, for example,
Writer paper, polyethylene coated paper, polypropylene synthetic
Transparent support with paper, reflective layer, or reflector
Body, eg glass plate, cellulose acetate, cellulosic
The porosity of nitrite or polyethylene terephthalate, etc.
Reester film, Polyamide film, Polycarbonate film
There are a nate film, a polystyrene film and the like. Most of the silver halide emulsion layer and the non-light-sensitive layer are transparent.
Normally, it is a hydrophilic colloid layer containing a hydrophilic binder.
ing. As the hydrophilic binder, gelatin,
Or acylated gelatin, guanidylated gelatin, flux
Phenylcarbamylated gelatin, phthalated gelatin, shea
Zera such as noethanol gelatin and esterified gelatin
A tin derivative is preferably used. As a hardening agent for hardening this hydrophilic colloid layer
Is, for example, chromium salt (chromium alum, chromium acetate,
Th), aldehydes (formaldehyde, glyoxer)
Compound, glutaraldehyde, etc.), N-methylol compound
Thing (dimethylol urea, methylol dimethyl hydantoy
Dioxane derivative (2,3-dihydroxydio
Active vinyl compounds (1,3,5-triacryl)
Royl-hexahydro-s-triazine, 1,3-vinyl
Sulfonyl-2-propanol, etc.), active halogenation
Compound (2,4-dichloro-6-hydroxy-s-triazi
), Mucohalogenates (mucochloric acid, mucofe
(Noxic acid, etc.), etc., alone or in combination
Used. In the present invention, the light-sensitive material uses a coupler as a high-boiling organic solvent.
So-called oil pro that contains the dispersed ones
This is especially effective in the case of tect type. This high boiling organic
As a solvent, organic acid amides, carbamates, ester
, Ketones, urea derivatives, especially dimethylphthale
, Ethyl phthalate, di-propyl phthalate,
Di-butyl phthalate, di-n-octyl phthalate,
Diisooctyl phthalate, diamyl phthalate, dino
Phthales such as nyl phthalate and diisodecyl phthalate
Acid ester, triclenzel phosphate, trife
Nyl phosphate, tri (2-ethylhexyl) phosphite
Phosphorus such as phosphate and trisononyl phosphate
Acid ester, dioctyl separate, di- (2-ethyl
Hexyl) sebacate, diisodecyl sebacate, etc.
Sebacate ester, glycerol tripropione
Glycerin such as glycerol and glycerol tributyrate
Stell, other, adipic acid ester, glutaric acid
Steal, succinate, maleate, huma
Acid ester, citric acid ester, di-tert-amyl
Phenol, phenol such as n-octylphenol
The effect of the present invention is great when a derivative is used. In the color development in the present invention, aromatic primary amine color development is used.
An image base is used, and various color photographic prints are used as the developing base.
Known items that are widely used in
Included. These developers are aminophenol-based and
A p-phenylenediamine derivative is included. these
Compounds are more stable than free and are generally in salt form, eg
Used in the form of hydrochloride or sulphate. Also these changes
In general, the amount of the compound is about 0.1 g to about 30 g for the color developer 1.
, About 1 g to about 15 for Color Developer 1
Use at a concentration of g. Examples of the aminophenol-based developer include o-amino.
Phenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-Oxy-3-amino-1,4-dimethylbenzene, etc.
included. Particularly useful aromatic primary amine color developing agents are N, N'-
A dialkyl-p-phenylenediamine compound,
Alkyl and phenyl groups can be replaced by any
May be. Among them, examples of particularly useful compounds
NN′-diethyl-p-phenylenediamine hydrochloride,
N-methyl-p-phenylenediamine hydrochloride, N, N-di
Methyl-p-phenylenediamine hydrochloride, 2-amino-
5- (N-ethyl-N-dodecylamino) -toluene,
N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate, N-ethyl-N
-Β-hydroxyethylaminoaniline, 4-amino-
3-methyl-N, N'-diethylaniline, 4-amino-
N- (2-methoxyethyl) -N-ethyl-3-methyl
Aniline-p-toluene sulfonate, etc.
You can read it. The color developer contains the above-mentioned aromatic primary amine color developer.
In addition to the various components normally added to color developers,
Minutes, for example sodium hydroxide, sodium carbonate, carbonate
Alkaline agents such as helium, alkali metal thiocyanates
Salt, alkali metal halide, benzyl alcohol,
Optional inclusion of water softeners and thickeners
You can also Aromatic primary amine color development as color developing agent
The pH value of a color developer using a developing agent is usually 7 or more.
Most commonly about 10 to about 13. Organic acid ferric iron complex used in the bleach-fixing solution used in the present invention
As a free acid with a salt molecular weight of less than 280,
Preferred are boric acid compounds and polyphosphonic acid compounds
Of these, the former is more preferable and
The compound represented by the general formula [IV] is preferable. General formula (IV)Where R₆Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, carbon
A hydroxyalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms
Shows a Coxy group or a carboxyalkyl group having 1 to 4 carbon atoms.
You Particularly preferred A is methyl group, hydroxyethyl group,
A carboxymethyl group, a butyl group and a hydrogen atom. For polyphosphonic acid compounds(Where B₁And B₂Are hydrogen atom, hydroxy group, and
It represents a alkyl group or an amino group. ) Is included. Typical examples of the above free acids are shown below, but the free acids are not limited to these.
Yes. (Molecular weight in parentheses) (1) Nitrilotriacetic acid (191.14) (2) Nitrilodiacetate propionic acid (205.17) (3) Iminodiacetic acid (133.10) (4) Iminodimethylenephosphonic acid (204.98) (5) N-methyliminodiacetic acid (147.063) (6) Iminodipropionic acid (161.074) (7) N- (3.3-dimethylbutyl) iminodiacetic acid (21
7.12) (8) Hydroxyethyliminodipropionacetic acid (205.
10) (9) Hydroxypropyliminodiacetic acid (191.09) (10) Methoxyethyliminodiacetic acid (191.09) (11) N- (carbamoylmethyl) iminodiacetic acid (190.09)
08) (12) Aminoethyliminodiacetic acid (179.08) (13) β- (N-trimethylammonium) ethylimi
Nodiacetate cation (219.12) (14) Phosphonomethyliminodiacetic acid (227.04) (15) Phosphonoethyliminodiacetic acid (241.14) (16) Sulfoethyliminodiacetic acid (241.14) (17) Hydroxyethyliminodiacetic acid (177.16) (18) Dihydroxyethylglycine (163.17) (19) Nitrilotripropionic acid (233.22) (20) Ethylenediaminediacetic acid (176.17) (21) Carboxyethyliminodiacetic acid (205.08) (22) N, N'-ethylenediamine Diacetic acid (172.08) (23) N, N'-di (hydroxyethyl) ethylenediami
Diacetic acid (264.13) (24) Ethylenediaminedipropionic acid (277.15) (25) Hydroxyethylethylenediaminetriacetic acid (27
8.26) (26) 1-hydroxyethylidene-1,1-diphosphonic acid
(205.97) (27) Hydroxymethylidene diphosphonic acid (191.96) (28) 1-Aminoethylidene-1,1-diphosphonic acid (20
3.98) (29) 1-aminopropylidene-1,1-diphosphonic acid (2
17.99) The ferric organic acid complex salt used in the present invention is of one type and
Combinations of more than one species can be used. The concentration is
Depending on the amount of silver and the silver halide composition of the light-sensitive material
It is necessary to select, but usually 2 x 10 per liquid used^-2
The range of 2 to 2 mol is preferable, and the range of 0.1 to 1.0 is more preferable.
The range is le. The bleach-fixing solution in the present invention contains the above organic acid as a bleaching agent.
Compounds other than ferric complex such as free acid having a molecular weight of 280 or more
The above organic acid can contain ferric iron complex salt,
The amount is 50 mol% or less of the total amount of the bleach, and 10 mol% or less
Preferably there is. Thiosulfate is the preferred fixer in the bleach-fix solution.
Good Thiosulfates are preferably alkali metal salts and salts.
Ammonium salts such as potassium thiosulfate and thiosulfate.
Examples thereof include sodium acid salt and ammonium thiosulfate. So
The concentration of 5g / l or more, may be in the range that can be dissolved, but preferably
It is in the range of 40 to 250 g / l. In the present invention, the bleach-fixing solution contains sulfite.
Is preferred. As sulfites, sodium sulfite,
Potassium sulfate, ammonium sulfite, ammonium bisulfite
Um, potassium bisulfite, sodium bisulfite, metabisulfite
Sodium sulfite, potassium metabisulfite, metabisulfite
Mmonium, hydrosulfite, glutaraldeh
Dobis sodium bisulfite, succinic aldehyde bis heavy acid
Compounds such as sodium sulfite can be used, but
Any compound can be used as long as it is a compound that releases an ion. 1x10 of the above sulfite in the bleach-fix solution^-3~ 0.1 mol / l included
Preferably. The bleach-fixing solution of the present invention includes boric acid, borax and sodium hydroxide.
, Potassium hydroxide, sodium carbonate, potassium carbonate,
Sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate
There are various pH protective agents such as um and ammonium hydroxide
Alternatively, two or more kinds may be combined and contained.
Furthermore, various optical brighteners, antifoaming agents or surface active agents
A sex agent can also be included. Also hydroxyl
Bisulfite addition of amine, hydrazine and aldehyde compounds
Preservatives for substances, organic chelates such as aminopolycarboxylic acids
Agents or stabilizers such as nitroalcohol and nitrate,
Tanol, dimethylsulfamide, dimethylsulfoxide
It is possible to appropriately contain an organic solvent and the like. Well
In addition, JP-A-46-280, JP-B-45-8506, 46-556,
Belgian Patent No.770,910, Japanese Patent Publication No.45-8836, No.53-985
No. 4, JP-A-54-71634 and JP-A-49-42349.
Various bleaching accelerators can be added. The bleach-fix solution used in the present invention has a pH of 4.0 or higher.
However, it is preferably pH 5.0 or more and pH 9.5 or more, more preferably
In other words, it is pH 6.0 or more and pH 8.5 or less. Processing temperature is below 80 ℃
3 ° C or higher than the temperature of the processing solution in the color developing tank, preferably
It is used at a temperature lower than 5 ℃, but preferably below 55 ℃
Use with reduced evaporation. In the present invention, processing by bleach-fixing and subsequent replacement with water washing
Treating with a stabilizing solution means bringing it to the frontmost tank for stabilization treatment.
The concentration of the fixer or bleach-fixer in the tank is 1/200
If it does not fall below, single or multiple tanks
Very short rinsing by formula, auxiliary water washing and water washing
This means that a treatment such as an acceleration bath may be performed. In the present invention, a stabilizing solution as a substitute for washing with water is a treatment using a bleach-fixing solution.
Immediately after the stabilization process, the stabilization process was performed
A processing solution for stabilizing treatment. In the present invention, the stabilization treatment may be performed in one tank or multiple tanks without any problem.
It can be used, but is preferably 1 to 4 tanks. The present invention is applicable to the case where the stabilizing bath replacement stabilizing solution replenishment amount is small.
The effect is large, and the replenishment amount of the photosensitive material
Range of 1 to 50 times the amount brought in from the previous bath per unit area
Is preferable, and the effect of the present invention is particularly preferable in the range of 2 to 20 times.
Is remarkable. The anti-mildew agent should be contained in the stabilizing solution for washing water replacement of the present invention.
Is preferred. Antifungal agent preferably used is hydroxy
Benzoic acid compounds, alkylphenol compounds, thia
Zol compounds, pyridine compounds, guanidine compounds
Compounds, carbamate compounds, morpholine compounds, quaternary
Phosphonium compounds, ammonium compounds, urea compounds
Compounds, isoxazole compounds, propanolamine
Compounds, sulfamide derivatives and amino acid compounds
is there. The hydroxybenzoic acid compound is hydroxybenzoic acid.
Methyl as an ester compound of acid and hydroxybenzoic acid
Ruester, ethyl ester, propyl ester, butyrate
And the like, but preferably hydroxybenzoic acid
N-butyl ester, isobutyl ester, propyl
Esters, more preferably the hydroxybenzoic acid
It is a mixture of three acid esters. Alkylphenol compounds have an alkyl group of C1-6
It is a compound that waits for an alkyl group as a substituent.
Preferred phenolic compounds are orthophenol,
Tocyclohexylphenol. A thiazole-based compound has a nitrogen atom and sulfur atom in the five-membered ring.
A compound having a child, preferably 1,2-benzisothiazole
Azolin-3-one, 2-methyl-4-isothiazoline 3
-One, 2-octyl-4-isothiazolin-3-one, 5
-Chloro-2-methyl-4-isothiazolin-3-one,
2- (4-thiazolyl) benzimidazole. Pi
The lysine compound is specifically 2,6-dimethylpyridine,
2,4,6-trimethylpyridine, sodium-2-viridine
Thiol-1-oxide and the like, but preferably
Um-pyridinethiol-1-oxide. The guanidine compounds are specifically cyclohexidine and
Lihexamethylene Biguanidine Hydrochloride, Dodecyl Guani
Gin hydrochloride, preferably dodecylguanidine and
And its salt. The carbamate compound is specifically methyl-1- (butyrate).
Lucabamoyl) -2-benzimidazole carbamay
And methyl imidazole carbamate. The morpholine compound is specifically 4- (2-nitrobutyrate).
) Morpholine, 4- (3-nitrobutyl) morpholine
Etc. Quaternary phosphonium compounds are tetraalkylphosphonium
There are various salts, such as tetra-alkoxyphosphonium salt, but
More preferably, the tetraalkylphosphonium salt is more specific.
The preferred compound is tri-n-butyl-tetradecylphosphoni
Umchloride, tri-phenyl nitrophenylphos
There is honium chloride. The quaternary ammonium compound is specifically benzalkonium
Salt, benzethonium salt, tetraalkylammonium
There are salts and alkyl viridinium salts.
Rudimethylbenzyl ammonium chloride, didecyl
Dimethylammonium Croyde, Laurylpyridinium
There are Croydes. The urea-based compound is specifically N- (3,4-dichlorophenyl)
) -N '-(4-chlorophenyl) urea, N- (3-
Trifluoromethyl-4-chlorophenyl) -N'-
(4-chlorophenyl) urea and the like. The isoxazole-based compound is specifically 3-hydroxy-
5-methyl-isoxazole and the like. Propanolamine-based compounds include n-propanols
There are isopropanols, specifically DL-2-benz
Luamino-1-propanol, 3-diethylamino-1-
Propanol, 2-dimethylamino-2-methyl-1-
Propanol, 3-amino-1-propanol, isop
Lopanolamine, diisopropanolamine, N, N-
Dimethyl-isopropanolamine and the like. The sulfamide derivative is specifically fluorinated sulfamide.
De, 4-chloro-3,5-dinitrobenzene sulfami
De, sulfanilamide, acetosulfamine, sulf
Pyridine, sulfaguanidine, sulfathiazo
Le, sulfadiazine, sulfamelazine, sulfame
Tadine, sulfisoxazole, homosulfami
, Sulfisomidine, sulfaguanidine, sulfa
Methizole, sulfapyrazine, phthalisosulfaty
Examples include azole and succinylsulfathiazole. The amino acid compound is specifically N-lauryl-β-ara.
There is nin. Among the above antifungal agents, the antifungal agent is preferably used in the present invention.
Compounds are pyridine compounds, guanidine compounds and
And quaternary ammonium compounds. To alternative treatment liquid for washing
The amount of the antifungal agent added is 0 per 1 liter of the water washing alternative treatment.
The range of 002g ~ 50g is preferable, more preferably 0.005g ~ 1
It is in the range of 0 g. The crack represented by the general formula [V], [VI] or [VII]
Among the chelating agents, the chelating agent preferable in the present invention is as follows.
Compounds represented by any of the general formulas [XII] to [XXIII]
Is. General formula [XII] MmPmO₃m General formula [XIII] Mn +₂PnO₃n + 1 General formula (XIV) A₁-R_{twenty one}-Z₁-R_{twenty two}-COOH General formula (XV)In the formula, E is a substituted or unsubstituted alkylene group, cycloalkyl
Xylene group, phenylene group, -R₂₇-OR₂₇-,-R₂₇-OR₂₇OR₂₇-
Or -R₂₇Z₁R₂₇Represents-, Z₁Is> N-R₂₇-A₆Or> N-A₆The table
Then R_{twenty one}~ R₂₇Each represents a substituted or unsubstituted alkylene group.
Then A₁~ A₆Is hydrogen atom, -OH, -COOM or -PO₃M₂The table
, M represents a hydrogen atom or an alkali metal atom, and m is 3
Is an integer of 6 and n is an integer of 2 to 20. General formula [XVI] R₂₈N (CH₂PO₃M₂)₂ Where R₂₈Is lower alkyl group, aryl group, aralkyl
Group or nitrogen-containing 6-membered ring group (-OH, -OR or-as a substituent)
COOM may be present), M is a hydrogen atom or
Represents a Lucari metal atom. General formula (XVII)Where R₂₉~ R₃₁Is hydrogen atom, -OH, lower alkyl
(Unsubstituted or as a substituent -OH, -COOM or -PO₃M₂Have
B)₃~ B_FiveAre hydrogen atoms, -OH, -COOM,
-PO₃M₂Or-Mj₂Represents a hydrogen atom, lower alkyl
Group, -C₂H_FourOH or -PO₃M₂Represents, M is a hydrogen atom or ar
Represents a potassium metal atom, n₁And m₁Each represents 0 or 1. General formula (XVIII)Where R₃₂And R₃₃Are hydrogen atom, alkali metal atom,
C₁~ C₁₂Alkyl group of C₁~ C₁₂Alkenyl group or cyclic
Represents an alkyl group, M is as defined in the general formula [XVII]
Is. General formula (XXI)Where R₃₄Is C₁~₁₂Alkyl group of C₁~₁₂The alkoxy
Base, C₁~₁₂Monoalkylamino group, C₂~₁₂The Archi
Luamino group, amino group, C₁~_{twenty four}Allyloxy group, C₆~_{twenty four}
Represents an arylamino group and an amyloxy group of₁~ Q₃
Is -OH, C respectively₁~_{twenty four}Alkoxy group of aralkyloxy
Group, allyloxy group, -OM '₃(M 'represents a cation
), Amino group, morpholino group, cyclic amino group, alkyl group
Ruamino group, dialkylamino group, arylamino group or
Represents an alkyloxy group. General formula [XX]General formula (XXI)Where R₃₅, R₃₆, R₃₇And R₃₈Are hydrogen atom and halogen atom
Child, sulfonic acid group, substituted or unsubstituted carbon atom number 1 to 7
An alkyl group ofAlternatively, it represents a substituted or unsubstituted phenyl group. R₃₉, R₄₀,
R₄₁And R_{twenty two}Is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
Represents a kill group. General formula (XXII)Where R₄₃And R₄₄Is a hydrogen atom, a halogen atom or sulfo
Represents an acid group. General formula (XXIII)Where R₄₅And R₄₆Are a hydrogen atom, a phosphate group, and a carvone, respectively.
Acid group, -CH₂COOH, -CH₂PO₃H₂Or a salt thereof, X₁Is
Represents a hydroxyl group or its salt, W, Z₂And Y₁Are hydrogen atoms,
Halogen atom, hydroxyl group, cyano group, carboxylic acid group, phosphorus
Acid group, sulfonic acid group or their salts, alkoxy group
Or represents an alkyl group. Also m₂Is 0 or 1, n₂Is 1 to 4
, 1 is 1 or 2, p is an integer of 0 to 3, and q is 0 to 2.
Represents the integer. Of the chelating agent represented by the general formula [XII] to [XXIII]
The following are specific examples. [Exemplary chelating agent] (1) Na_FourP_FourO₁₂ (2) Na₃P₃O₉ (3) H_FourP₂O₇ (4) H_FiveP₃O_Ten (5) Na₆P_FourO₁₃  (15) (HOC₂H_Four)₂NCH₂COOH In the present invention, the general formula [XII], [XIII], [XVI] or
Is effective to use the chelating agent represented by [XVII].
is there. Particularly preferred chelating agents (1), (3),
(5), (31), (44), (46), (48), (81),
The chelating agent represented by (82) is used. this
These chelating agents can be used in combination of two or more.
It Any of the above general formulas [V] to [VII] used in the present invention
The chelating agent shown here is per wash stabilizing substitute solution
1 x 10^-FourIt can be added in the range of 1 mol to 1 mol.
2 x 10^-Four~ 1 x 10^-1Can be added in the molar range
Yes, more preferably 5 × 10^-Four~ 5 x 10^-2Add in molar range
Can be added. Desired to be added to the stabilizing solution as a substitute for washing used in the present invention
An example of the compound is an ammonium compound. These are the ammonium salts of various inorganic and organic compounds.
Supplied, but specifically ammonium hydroxide, bromide
Ammonium, ammonium carbonate, ammonium chloride,
Ammonium hypophosphite, ammonium phosphate, phosphorus
Ammonium acid, ammonium fluoride, acid fluoride
Monium, ammonium fluoroborate, ammonium arsenate
Um, ammonium hydrogen carbonate, ammonium hydrogen fluoride
System, ammonium hydrogen sulfate, ammonium sulfate, iodide
Ammonium, ammonium nitrate, ammonium pentaborate
System, ammonium acetate, ammonium adipate, lau
Ammonium phosphotricarboxylate, Ammonium benzoate
, Ammonium carbamate, ammonium citrate
System, ammonium diethyldithiocarbamate, formic acid
Ammonia, ammonium hydrogen malate, hydrogen oxalate
Ammonium, ammonium hydrogen phthalate, hydrogen tartrate
Ammonium, ammonium thiosulfate, ammonium sulfite
Um, Ammonium ethylenediaminetetraacetate, 1-Hydride
Roxyethylidene-1,1-diphosphonate ammonium,
Ammonium lactate, ammonium malate, maleic acid
Ammonium, ammonium oxalate, ammonium phthalate
Ni, ammonium picrate, pyrrolidine dithioca
Ammonium lumbamate, ammonium salicylate, co
Ammonium succinate, ammonium sulfanilate, liquor
Ammonium tartrate, ammonium thioglycolate, 2,
4,6, -trinitrophenol ammonium and the like.
These may be used alone or in combination of two or more. The amount of ammonium compound added is 0.00 per stabilizer.
It is in the range of 1 mol to 1.0 mol, preferably 0.002 to 0.2.
It is in the molar range. In the present invention, the stabilizing solution as a substitute for washing with water is used together with the chelating agent.
It is preferable to use a metal salt. Such metal salt
As Ba, Ca, Ce, Co, In, Mn, Ni, Pb, Sn, Zn, Ti, Zr, Al, Sr
Examples of metal salts include halides, hydroxides, and sulfuric acids.
Inorganic salts such as salts, carbonates, phosphates, acetates or water-soluble salts
It can be supplied as a rate agent. Stabilization liquid 1
Per 1 x 10^-Four~ 1-10^-2It is in the molar range. Other commonly known stabilizing bath additives include, for example,
For example, surfactants, organic sulfur compounds, onium salts, formalis
There are hardeners such as tin and chromium, but addition of these compounds
The loading is necessary to maintain the pH of the stabilizing bath according to the invention and
Poor stability and storage of color photographic images during storage
What compounds and what
It doesn't matter if you use them in combination. The pH of the alternative solution for washing with water in the present invention makes the present invention more effective.
In order to achieve, preferably in the range of 3.0-11.0
PH is more preferably in the range of 6.0 to 11.0, and particularly preferably
The pH is preferably in the range of 7.0 to 10.0. Washing alternative of the present invention
The pH adjusting agent that can be contained in the stabilizing solution is generally known.
You can use any of the alkaline or acid agents
Wear. The treatment temperature for stabilizing treatment is 15 ° C to 60 ° C, preferably 20 ° C.
The range of ~ 45 ℃ is good. Also, is the processing time a point of view for rapid processing?
The shorter the time, the better.
It is also preferably 1 to 3 minutes, and is suitable for multi-tank stabilization treatment.
In the case of
It is preferably long. 20% to 50% increase in treatment of the previous tank
It is desirable to process sequentially in time. Stabilization according to the invention
No rinsing is required after the treatment, but it is extremely short
Rinsing with a small amount of water and surface cleaning are required within the space
It can be arbitrarily performed. Supply of a substitute liquid for washing with water in the stabilization treatment process according to the present invention
When the method is a multi-tank counter current method, a post-bath
It is preferable to supply it to
Yes. Of course, it can also be processed in a single tank. The above compound
As a method of adding, add as a concentrated liquid to the stabilizing tank.
Or use a stabilizing solution as a substitute for rinsing that is supplied to the stabilization tank.
Add the above compounds and other additives, and wash this with water.
There are various methods such as whether to use the supply liquid for the constant replenisher.
However, they may be added by any addition method. Washing alternative stabilizer and bleach-fix used in the method of the present invention
In a known method from a processing solution containing a soluble silver complex salt such as a solution
You may recover silver. For example, the electrolysis method (French patent 2,299,
667), precipitation method (JP-A-52-73037)
Listed in German Patent No. 2,331,220), ion exchange method
(Unexamined Japanese Patent Publication No. 51-17114, German Patent No. 2,548,237
Detailed description) and metal substitution method (UK Patent 1,353,805)
Can be used effectively. The method of the present invention is applied to color negative paper, color positive
It is advantageous to apply it to super and reverse color paper
Is. [Examples] The present invention will be specifically described with reference to Examples below.
However, the embodiment of the present invention is not limited thereto. Example 1 An experiment was conducted with the following color paper, processing solution and processing steps.
It was. [Color paper] Polyethylene coated paper The following layers on the support
From the above to produce a light-sensitive material. The average molecular weight of polyethylene coated paper is 10
200 parts by weight of polyethylene with an average density of 0.95 and an average molecular weight of 0.95
2,000, mixed with 20 parts by weight of polyethylene with a density of 0.80
Add 6.8% by weight of anatase type titanium oxide to the product and press
Weight 170g / m according to extrusion coating method²High quality paper table
A 0.035 mm thick coating layer is formed on the front surface, and
A coating layer with a thickness of 0.040 mm is made of only chilen
Was used. On the polyethylene-coated surface of this support surface,
After pretreatment by Rona discharge, each layer is applied in sequence.
It was First layer: Blue-sensitive halo consisting of silver chlorobromide emulsion containing 80 mol% of silver bromide
In the silver genide emulsion layer, the emulsion is a zener per mol of silver halide.
Includes 350g of latin and has the following structure per mol of silver halide
Sensitizing dye2.5 x 10^-FourSensitized with mol (isopro
Pill alcohol), dissolved in dibutyl phthalate
Α- [4- (1-
Benzyl-2-phenyl-3,5-dioxo-1,2,4-tri
Azoridyl)] α-bivalyl-2-chloro-5- [γ-
(2,4-Di-t-amylphenoxy) butyramide] a
2 x 10 of cetoanilide per mol of silver halide^-Including mole
Amount of silver 330mg / m²Is applied so that Second layer: an ultraviolet absorber dissolved and dispersed in dibutyl phthalate
2- (2'-hydroxy-3 ', 5'-di-t-butyl
Ruphenyl) benzotriazole 2- (2'-hydroxy)
Ci-5'-t-butylphenyl) benzotriazole,
2- (2'-hydroxy-3'-t-butyl-5'-me
Tylphenyl) -5-chlorobenzotriazole and
2- (2'-hydroxy-3 ', 5'-di-t-butylphen
A mixture of phenyl) -5-chloro-benzotriazole 20
0 mg / m²2000mg / m gelatin in the gelatin layer containing²In
Is applied as. Third layer: edge-sensitive halo composed of silver chlorobromide emulsion containing 85 mol% of silver bromide
Silver genide emulsion layer, the emulsion being based on 1 mol of silver halide
Containing 450 g of gelatin, the following composition per mol of silver halide
Sensitizing dye2.5 x 10^-3Sensitized with dibutyl phthalate and
Dissolve reclindiphosphate in a 2: 1 mixed solvent
As a dispersed magenta coupler 1- (2,4,6-tri
Chlorophenyl) -3- (2-chloro-5-octadece
Nylsuccinimidoanilino) -5-pyrazolone halo
1.5 x 10 per mol of silver genide^-1Containing mol, silver amount 300mg
/ m²Is applied so that In addition, with an antioxidant
And 2,2,4-trimethyl-6-lauryloxy-7-t
-Octyl chroman content of 0.3 mol per mol of coupler
I had it. Fourth layer: UV absorber dissolved and dispersed in dioctyl phthalate
As 2- (2'-hydroxy-3 ', 5'-di-t-bu
Tylphenyl) benzotriazole, 2- (2′-hydr)
Roxy-5'-t-butylphenyl) benzotriazo
2- (2'-hydroxy-3'-t-butyl-5 '
-Methylphenyl) -5-chlorobenzotriazole
And 2- (2'-hydroxy-3 ', 5'-t-butylphenyl)
A mixture of phenyl) -5-chloro-benzotriazole
(2: 1.5: 1.5: 2) 500 mg / m²Gelatin layer containing gelatin
Chin amount 2000mg / m²Is applied so that Fifth layer: Red-sensitive halo consisting of silver chlorobromide emulsion containing 85 mol% of silver bromide
Silver genide emulsion layer, the emulsion being based on 1 mol of silver halide
Containing 500 g of gelatin, the following composition per mol of silver halide
Sensitizing dye2.5 x 10^-3Sensitized with mol dibutyl phthalate
Halogenated cyan couplers below dissolved and dispersed in
Formula 3.5 × 10 per mol of silver^-1Molar content, silver amount 300mg / m²
Is applied so that The fifth layer cyan coupler is an exemplary cyan coupler of the present invention.
Also, the following comparative couplers (1) and (2) are shown in Table-1.
I used each one. Comparative cyan coupler (1)Comparative cyan coupler (2)6th layer: Gelatin layer with a gelatin content of 1000 mg / m²Applied so that
Has been done. Silver halide milk used for each photosensitive emulsion layer (first, third and fifth layers)
The agent is prepared by the method described in JP-B-46-7772.
And chemistry using sodium thiosulfate pentahydrate, respectively.
4-hydroxy-6-methyl-1, as a sensitizer and stabilizer,
3,3a, 7-Tetrazaindene, Bis (vinyl) as a hardener
Sulfonylmethyl) ether and sapo as a coating aid
It contained nin. Photosensitivity prepared by changing only the cyan coupler as described above.
After exposure of materials (No. 1 to 9), depending on the next processing step and processing solution
Processed. Standard processing step [1] Color development 38 ° C 3 minutes 30 seconds [2] Bleach fixing 33 ° C 1 minute 30 seconds [3] Stabilization treatment 25 ° C to 35 ° C 3 minutes [4] Drying 75 ° C to 100 ° C Approximately 2 minutes Composition of processing solution <Color development tank solution> Benzyl alcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 1.3 g Sodium chloride 0.2 g Potassium carbonate 30.0 g 3-Methyl-4-amino-N-ethyl-N- (β -Meta
Sulfonamide ethyl) -aniline sulfate 5.5 g Optical brightener (diaminostilbene derivative) 1.0 g Hydroxylamine sulfate 3.0 g 1-Hydroxyethylidene-1,1-diphosphone 3 0.4 g Hydroxyethyliminodiacetic acid 5.0 g Chloride Magnesium hexahydrate 0.7 g 1,2-dihydroxybenzene-3,5-disulfonic acid-dina
Thorium salt 0.2 g Add water to make KOH and H₂SO_FourPH to 10.20. <Color development replenisher> Benzyl alcohol 20.0 ml Ethylene glycol 20.0 ml Potassium sulfite 3.0 g Potassium carbonate 30.0 g Hydroxylamine sulfate 4.0 g 3-Methyl-4-amino-N-ethyl-N- (β-meta
Sulfonamidoethyl) -aniline sulfate 7.5 g Optical brightener (diaminostilbene derivative) 2.5 g 1-Hydroxyethylidene-1,1-diphosphonic acid 0.5 g Hydroxyethyliminodiacetic acid 5.0 g Magnesium chloride hexahydrate 0.8 g 1,2-dihydroxybenzene-3,5-disulfonic acid-di-na
Thorium salt 0.3 g Add water to adjust to 1 and adjust pH to 10.70 with KOH. <Bleach-fixing tank liquid> Ferric complex salt of chelating agent in Table-1 80 g Chelating agent in Table-1 10 g Ammonium thiosulfate (70% soluble) 100 g Ammonium sulfite (40% dissolved) 27.5 ml Ammonium water or glacial acetic acid Adjust to pH 7.1 with
Add water to bring the total volume to 1. <Bleach-fixing replenisher> Ferric complex salt of chelating agent in Table-1 300g Chelating agent in Table-1 20g Adjust pH to 6.7 with potassium carbonate or glacial acetic acid and water.
Is added to bring the total amount to 1. <Bleach-fixing replenisher B> Ammonium thiosulfate (70% dissolution) 500 ml Ammonium sulfite (40% dissolution) 250 ml Chelating agent in Table-1 15 g Adjust pH to 5.3 with ammonia or glacial acetic acid and add water.
In addition, the total amount is 1. <Stabilizing tank replacement solution and replenishing solution> 5-chloro-2-methyl-4-isothiazolin-3-o
0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g ethylene glycol 1.0 g 2-octyl-4-isothiazolin-3-one 0.01 g Exemplified chelating agent (82) 3.0 g BiCl₃(45% aqueous solution) 0.65 g Ammonia water (25% ammonium hydroxide aqueous solution) 3.0 g Exemplified chelating agent (44) 1.5 g Water to 1 and H₂SO_FourAnd adjust pH to 8.0 with KOH. The amount of replenishment for each processing tank solution is
1 m²Per color development replenisher 190ml, bleach-fix replenisher A, B
50 ml each and 190 ml of stable replenisher alternative to washing with water. In addition, the stabilization processing bath of the automatic processor is
The first tank to the third tank is a stable tank, and the final tank is supplemented.
Fill and overflow from the last tank to the previous tank
Inflow, and this overflow liquid again
The multi-tank counter-current direction was used to flow into the tank. Also, for comparison, a process in which the stabilization process is replaced with a washing alternative
went. Stable against each of the obtained No. 1 to No. 9 photosensitive materials
For samples treated with acidification and washing with running water at 70 ° C, 50% RH
Forced deterioration test using a high-humidity high-temperature tank and a xenon arc lamp
Replace the forced deterioration test every other day and store for 4 weeks
It was Optical density meter PDA-65 (small
Sairoku Photo Industry Co., Ltd.) cyan color measured with red light
The color fading rate was calculated. The results are shown in Table-1.As is clear from the results shown in Table-1, the system of the present invention of Nos. 8 and 9 is
Uses a light-sensitive material containing an uncoupler and has a low molecular weight.
Bleach containing a ferric salt of a chelating agent as a bleaching agent
Those treated with a fixer have a very low cyan dye fading rate and are extremely
And is particularly excellent as a bleaching agent, represented by the general formula [IV]
It is highly preferred to use a ferric iron complex salt of the free acid
I understand. [Effects of the Invention] The method of the present invention requires the use of washing water in the color development processing.
There is no need, so an energy control that regulates the temperature of the flush water
A color development process that does not require a strike and has a low pollution load.
By reason, the cyan dye image of a long-term storage
Provides a color photographic image with improved photobleachability.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP 59-184343 (JP, A) JP 59-149364 (JP, A) JP 59-184344 (JP, A) JP 61- 75353 (JP, A) JP-A-57-8543 (JP, A) JP-A-58-134636 (JP, A) JP-A-58-14834 (JP, A)

Claims (2)

[Claims] 1. A ferric complex salt of an organic acid having a free acid having a molecular weight of less than 280 immediately after color development of a silver halide color photographic light-sensitive material containing a cyan coupler represented by the following general formula [I]. Is treated with a bleach-fixing solution, and subsequently treated with a water-washing alternative stabilizing solution containing a chelating agent represented by the following general formula [V], [VI] or [VII] without substantially washing with water. A method of forming a color photographic image. General formula [I] [In the formula, one of R and R ₁ is a hydrogen atom, the other is a linear or branched alkyl group having at least 2 to 12 carbon atoms, and X is a hydrogen atom or an aromatic primary amine color developing agent. R ₂ represents a group that is split off by a coupling reaction with an oxidant.
Represents a ballast group. ] General formula [V] A-C00M General formula [VI] B-PO ₃ M ₂ General formula [VII] [Wherein A and B each represent a monovalent group or atom,
D represents an aromatic ring or a heterocycle which may have a substituent,
M represents a hydrogen atom or an alkali metal atom. ] 2. The method for forming a color photographic image according to claim 1, wherein the free acid of the ferric organic acid complex salt is a compound represented by the following general formula [IV]. General formula (IV) [In the formula, R ₆ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a carboxyalkyl group having 1 to 4 carbon atoms. . ]