JP2739314B2 - Processing method of silver halide color photographic light-sensitive material with improved image storability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial applications]   The present invention relates to a method for processing a silver halide color photographic light-sensitive material.
More specifically, antioxidants that are not toxic to the human body
Even if the used color developing solution is used, it may adversely affect the developability.
Anhydrous washing that significantly improves dye image stability
The present invention relates to a processing method suitable for processing of a method. [Conventional technology]   In recent years, in the industry, silver halide color photographic
Quick processing of optical materials is possible, and processing stability
Technology that can provide excellent and stable photographic characteristics is desired.
You.   That is, silver halide color photographic materials are
Running processing with an automatic processor
Has been implemented,
As part of the development process,
Is required to be returned to the user.
It is even required to return in a matter of hours
ing.   In recent years, stores such as photo shops and supermarkets have
Automatic developing machine installed in the area, photosensitive material
It is required to process and return the fee on the spot
I have.   In addition, copying equipment that irradiates the original with light and copies it on photosensitive material
Devices have become available on the market.
However, the time required to develop the photosensitive material on which the original was copied is
It must be short, rather
Request immediate access to the copied photosensitive material.
It is the present situation.   With the demand for speeding up,
Intensively with an automatic processor installed in a simple laboratory
Due to the tendency to process large amounts of color light-sensitive materials, photo shops and
Ultra-small simple automatic developing machine in stores such as permarkets
For on-the-spot processing, or even silver halide
Color photo-sensitive material development system installed in copiers
Recently, the tendency to make color copies indoors has become particularly remarkable.
It has become.   However, there are serious problems with this trend.
It turned out to be. In other words, color
When color developing a photosensitive material, the color developing solution
Sulfuric acid to prevent loss of capacity due to air oxidation
Salts and hydroxylamine have been used. However,
Droxylamine is harmful to the human body (P.G.Stecher.
`` The Merck Index-An Encyclopedia of Chemical and
 Drugs "8th Ed (1953)), Poisonous and Deleterious Substances Control Law
Even hydroxylamine and its water-soluble salts are designated as deleterious substances
Have been. Therefore, processing in large laboratories
Even if they are used, care must be taken when handling them.
Especially for amateurs who do in-store processing.
There are many titles. Therefore, in-house processing and color development at stores
Pollution when performing color copying with the formula
Due to the above problems, the development of antioxidants instead of hydroxylamine
Departure is strongly desired.   As an antioxidant instead of hydroxylamine, 2-A
Nirinoethanol and dihydroxyalkene are US patents
Nos. 3,823,017 and 3,615,503 respectively.
However, all of these compounds are unstable themselves.
And there is no effect of preventing color fog.   On the other hand, hydroquinone or N-alkyl-p-a
Developing solution containing minophenol as a developing agent
Saccharol (sucrose) as an antioxidant
As is known, sucrose is an aromatic primary amine
Is used as an antioxidant in color developing solutions containing
Little effect.   In addition, ascorbic acid and its derivatives are
Known as an antioxidant for liquid and color developing solutions,
These have the disadvantage that they hinder color development and cause a decrease in color density.
Color developing solution is inferior to hydroxylamine.   Further, α-hydroxy aromatic compounds described in JP-A-52-7729
Alcohol Hydroxam oxidation described in JP-A-52-27638
Α-aminocarbonyl compound described in JP-A-52-143020
And monosaccharides described in JP-A-52-102727, JP-A-52-140324
The disclosed amino acid derivatives are disclosed.   When large amounts of monosaccharides and amino acid derivatives are used at room temperature,
And shows considerable preservation,
It also has unfavorable pollution characteristics.   Representative compounds of α-aminocarbonyl compounds include
D-glucosamine hydrochloride is known, but this compound
Is less preservative than hydroxylamine.   Hydroxamic acid compounds are hydroxyamine
Although it has the same level of preservation as
There is a disadvantage that the color development density tends to decrease.   As mentioned above, the conventionally used hydro
Considered as an antioxidant (preservative) to replace xylamine
The above materials that have been used have insufficient preservative properties or
Therefore, there are problems such as decomposition and lowering of the coloring efficiency.
At present, it has not been put to practical use until this stage.   Also, derivatives of hydroxylamine as antioxidants
JP-A-54-3532, JP-A-56-94349, JP-A-61-43742, etc.
Is known by:   The inventors of the present invention have proposed a technology relating to the speeding up of the above processing.
Applicable to automatic developing machines and copiers installed in stores
As a development processing method, finally treat with water
Replacement of hydroxylamine in washing-free treatment methods
As a result of a thorough examination of the product,
Droxylamine derivatives replace hydroxylamine
No problem as described above, and the color developer has a high preservation ability.
However, it was found that hydroxy
Fixing solution or color developing solution using
Is a processing solution having a fixing ability, which is a bleach-fixing solution.
Rinse with water instead of washing solution
(Referred to as stabilization processing), the generated cyan dye image
Storage stability is likely to deteriorate, such as processed photographic prints
Is stored in an album for a long time, the cyan dye image
The present inventors found that the concentration of
Etc. headed. This is completely unexpected by the present inventors.
Was that.   The present inventors have intensively studied to solve such a problem.
As a result, the present invention has been accomplished. [Object of the invention]   The object of the present invention is to provide an antioxidant for hygiene and pollution.
Other alternative oxidations without problematic hydroxylamine
No deterioration in photographic quality as described above in the inhibitor
Good photographic quality images can be obtained by the washing stabilization process instead of washing.
To provide a method for processing silver halide photographic light-sensitive materials
That is. [Configuration of the invention]   An object of the present invention is to provide a halo having a silver chloride content of 70 mol% or more.
Silver halide containing at least one silver gemide emulsion layer
A color photographic light-sensitive material is prepared by using a hydrid represented by the following formula [I].
Color development processing with a color developer containing roxylamines
After processing with a processing solution having a fixing ability,
Ten^-FourMore than 1 × 10^-2Washing with less than mol soluble iron salt
Silver halide powder characterized by being processed with an alternative stabilizer
This is achieved by a method for processing color photographic light-sensitive materials. General formula [I]   Where R¹And R^TwoEach has a hydrogen atom or a substituent
Represents an optionally substituted alkyl group. Where R¹And R^TwoSame as
It cannot be a hydrogen atom.   Hereinafter, the present invention will be described in detail.   Widely used with sulfites as antioxidants
Hydroxylamine has been
Many alternatives have been considered because of their virulent and harmful nature.
However, as mentioned above, acids
Antioxidants have some effect of preserving the color developing agent
The density of the dye formed during color development of
It loses its effect completely or costs
Had high problems and had considerable problems.   The hydroxylamide represented by the general formula [1] of the present invention
Derivatives have excellent color developing agent preservation ability and
It is an excellent antioxidant with little decrease in color density. I
However, the hydroxy represented by the general formula [1] of the present invention
Silamines are processed with a processing solution that has fixing ability after color development
After that, when treated with an alternative washing solution with water washing with anhydrous washing,
The decrease in cyan dye concentration after treatment is
Remarkably large.   No reduction in cyan dye concentration for hydroxylamine
Not seen, cyan dye depending on N-alkyl number
Because of the difference in density reduction, it is probably
The above hydroxylamine derivative remains in
Flow from the photosensitive material because
Output, and the density of the cyan dye image decreases over time.
It is considered to have been caused.   The present inventors have studied diligently to solve these problems.
As a result, the soluble iron salt was converted to a water-washing alternative stabilizer at a certain concentration or higher.
The above problem can be solved effectively by containing
And completed the present invention.
You.   The present invention will be described in more detail.
Color developing solution to conventional hydroxylamine sulfate
Instead, a compound represented by the general formula [1] is used.
You.   In the general formula [1], R₁And R_TwoHaving a substituent represented by
The alkyl group which may be preferably has 1 to 5 carbon atoms,
More preferably, it has 1 to 3 carbon atoms. Expressed by the formula
R₁And R_TwoAre both alkyl groups
Is preferred.   In the general formula [1], R₁And R_TwoArchi represented by
Substituents which the aryl group may have include sulfo group,
Droxyl group, alkoxy group (methoxy group, ethoxy
Group, propyloxy group, etc.), carboxyl group, amino group
And the like, for example, US Patent 3,287,
No. 125, 3,293,034, 3,287,124, etc.
And hydroxylamines.   Hereinafter, preferred specific examples represented by the general formula [1]
1 shows a compound.   The compound represented by the general formula [1] is usually hydrochloride, sulfuric acid
Salt, p-toluenesulfonate, oxalate, phosphoric acid
Used in the form of salts such as salts and acetates.   The concentration of the compound of the present invention in the color developer is usually a preservative.
The same concentration as hydroxylamine used as
For example, 0.2 g / -50 g / is preferably used, and more preferably.
Preferably 0.5 g / ~ 30 g /, more preferably
1.0 g / ~ 20 g /. The compounds of the present invention may be of two kinds or
May be used in combination to maintain the preservation of the color developing agent
Arbitrarily in terms of image quality and image storability.
Good.   Color developing agent used in the color developing solution used in the present invention
As a p-phenylenediamine having a water-soluble group
Compounds are preferred from the viewpoint of achieving the object of the present invention.   P-phenylenediamine compound having a water-soluble group
Is an aqueous solution of N, N-diethyl-p-phenylenediamine or the like.
Compared to para-phenylenediamine compounds without functional groups
In addition, there is no contamination of the photosensitive material and the skin
Not only has the advantage of being difficult to irritate,
Combination with the compound represented by the general formula [1] in the invention
In this way, the object of the present invention can be achieved efficiently.
Can be.   The water-soluble group is a p-phenylenediamine compound
Having at least one amino group or benzene nucleus
And specific water-soluble groups include   − (CH_Two) N-CH_TwoOH,   − (CH_Two) M-NHSO_Two− (CH_Two) N-CH_Three,   − (CH_Two) MO- (CH_Two) N-CH_Two,   − (CH_TwoCH_TwoO) nC_ThreeH_{2m + 1} (M and n each represent an integer of 0 or more.)   -COOH, -SO_ThreeH and the like are preferred.   Specific examples of the color developing agent preferably used in the present invention
The compounds shown below are shown below.   Illustrative color developing agents   Among the color developing agents exemplified above, preferred for use in the present invention.
It is preferable that the example Nos. (A-1), (A-2), (A-
3), (A-4), (A-6), (A-7) and (A
-15), particularly preferably (A-
1).   The above color developing agents are usually hydrochloride, sulfate, p-toluene.
It is used in the form of salts such as ene sulfonate.   Color developing agent having a water-soluble group used in the present invention
Is usually 1 × 10 per color developer^-3~ 2 × 10^-1Mole of
It is preferable to use it within the range, but from the viewpoint of rapid processing
2.0 × 10 per color developing solution^-3~ 2 × 10^-1Mole range
More preferred.   In the color developer used in the present invention, in addition to the above components,
The developer component can be contained.   As an alkali agent, for example, sodium carbonate, potassium carbonate
Sodium, potassium hydroxide, silicate,
Sodium metaborate, potassium metaborate, phosphoric acid 3
Sodium, potassium triphosphate, borax etc.
In combination, without precipitation, maintaining pH stabilizing effect
It can be used together within the range. Further dispensing needs
From or for the purpose of increasing the ionic strength, etc.
Disodium hydrogen phosphate, dipotassium hydrogen phosphate, heavy carbon
Various salts such as sodium silicate, potassium bicarbonate and borate
Can be used.   Also, if necessary, inorganic and organic antifoggants
Can be added.   Also, a development accelerator can be used if necessary.
You. As development accelerators, U.S. Pat.No. 2,648,604,
No. 3,671,247, each represented by JP-B-44-9503
Certain pyridinium compounds and other cationic compounds
Substances, cationic dyes such as phenosafranine,
Neutral salts such as lium, U.S. Patent Nos. 2,533,990 and 2,5
No. 31,832, No. 2,950,970, No. 2,577,127, and
Polyethylene glycol described in JP-B-44-9504 and
Nonionic compounds such as derivatives and polythioethers
Organic solvents and organic solvents described in JP-B-44-9509.
, Ethanolamine, ethylenediamine, diethanol
Luminamine, triethanolamine and the like. Also rice
Benzyl alcohol described in National Patent No. 2,304,925
, Phenethyl alcohol, and acetyl
Len glycol, methyl ethyl ketone, cyclohexano
, Thioethers, pyridine, ammonia, hydrazine
And amines.   Further, the color developer used in the present invention may contain
, Ethylene glycol, methyl cellosolve, methanol
, Acetone, dimethylformamide, β-cyclodex
String, Other JP-B Nos. 47-33378 and 44-9509
The compounds described in the publication are used to increase the solubility of developing agents.
It can be used as an organic solvent.   In addition, the use of auxiliary developers with developing agents
it can. As these auxiliary developers, for example, N-methyl
Le-p-aminophenol hexalfate (Metho
), Phenidone, N, N'-diethyl-p-aminophen
Nol hydrochloride, N, N, N ', N'-tetramethyl-p-fe
Nilendiamine hydrochloride, etc.
Usually, the addition amount is preferably 0.01 g to 1.0 g /. Besides this
As required, mixed couplers, fogging agents, colored
Coupler, development inhibitor releasing type coupler (so-called DIR
Coupler) or a development inhibitor releasing compound, etc.
You can also.   Furthermore, other stain inhibitors, sludge prevention
Various additives such as an agent and an overlay effect promoter can be used.
You.   Each component of the color developing solution is sequentially added to water as a solvent.
It can be prepared by adding and stirring. In this case water
The highly soluble components are
It can be added by mixing with an organic solvent or the like. Again
Generally, a plurality of components that can coexist stably
Concentrated aqueous solutions, or those previously prepared in small containers in the solid state
Is added to water and stirred to prepare a color developer of the present invention.
It can be.   In the present invention, the color developing solution is used in an arbitrary pH range.
It can be used, but it should be pH 9.5 to 13.0 from the viewpoint of rapid processing.
Are preferably used at pH 9.8 to 13.0.
You.   In the present invention, the processing temperature for color development is 30 ° C. or lower.
Above, 50 ℃ or less, the higher the processing temperature, the faster the processing and
It is preferable because rapid decolorization is possible, but on the contrary, preservation is deteriorated
There is also a problem that it is easy to perform, more preferably 30 ℃ or more,
It is in the range of 45 ° C or less.   The color development time is about 3 minutes 30 seconds conventionally used in general
The effect of the present invention is more remarkable as the processing time is shorter.
Thus, the present invention is suitable for rapid processing.   After processing with a processing solution having a fixing ability in the present invention,
Treating with a stabilizing solution instead of washing means that it is held in the tank before stabilization.
Fixing solution or bleach-fixing solution concentration in the tank
Single tank or multiple tanks as long as is not less than 1/200
Very short rinsing by tank countercurrent method, auxiliary water washing and
And that treatment such as a washing promotion bath may be performed.
Yes, in the present invention at least 1.0 × 10^-FourMol /
At the above concentrations, soluble iron salts are present in
Is a prerequisite for achieving the present invention.   1.0 × 10 soluble iron salt^-FourMost if less than mol /
Or completely contribute to the stability of the cyan dye image over time.
Not less than 1.0 × 10^-FourMol / or more soluble iron salt
is necessary. The upper limit of the soluble iron salt concentration of the present invention is 1 × 10^-2
Mol /, exceeding this upper limit, the concentration of soluble iron salt
Is high, yellow stain tends to occur,
Is a major problem in color photographic quality.   In the present invention, the treatment with the washing substitute stabilizer is the fixing ability.
Immediately after processing with a processing solution that has
Treatment for stabilization without substantial water washing
Refers to the treatment liquid used for the stabilization treatment, and a stabilizing liquid instead of a washing liquid.
The treatment tank is called a stabilizing bath or a stabilizing tank.   In the present invention, stabilization is not a problem in one or multiple tanks.
But preferably 1 to 4 tanks
You.   The present invention requires a small amount of replenishment of a stabilizing bath with a water washing alternative stabilizer.
In this case, the effect is great, and the replenishment amount is
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 within a range of 2 to 20 times.
This is particularly noticeable.   The soluble iron salt used in the present invention is a water-soluble iron salt.
Inorganic or organic salts may be used, and ferrous salts may be used
Iron salts may be used.   The components of the washing stabilizing solution are basically the same as the soluble iron salt.
May be water alone, but various compounds may be added.
The compounds that can be preferably used in the present invention include
Agents, ammonium salts, chelating agents and metal salts.   Antifungal agents are particularly preferred in the washing-substitute stable liquid of the present invention.
Used not only for anti-bicycle effect, but also for cyan dye image
Also preferred for stabilization. The fungicide used is Hido
Roxybenzoic acid compounds, phenol compounds, thiazo
Compounds, pyridine compounds, guanidine compounds
Products, carbamate compounds, morpholine compounds, quaternary
Phosphonium compounds, ammonium compounds, urea compounds
Compound, isoxazole compound, propanolamine
Compounds, sulfamide derivatives, amino acid compounds and
It is a benzotriazole compound.   The hydroxybenzoic acid-based compound is hydroxybenzoic.
As an ester compound of carboxylic acid and hydroxybenzoic acid,
Cyl ester, ethyl ester, propyl ester, butyl ester
Butyl esters and the like, but preferably
N-butyl ester, isobutyl ester,
And more preferably the hydroxybenzoate.
It is a mixture of three kinds of fragrances.   Alkylphenol compounds are alkyl groups, halogenated
Nitro group, hydroxyl group, carboxylic acid group, amino group,
Phenolic compounds which may have an aryl group or the like as a substituent
Product, preferably orthophenylphenol,
Tocyclohexylphenol.   Thiazole compounds have a nitrogen atom and a sulfur atom on a five-membered ring.
A compound having an atom, preferably 1,2-benziso
Thiazoline 3-one, 2-methyl-4-isothiazoline
3-one, 2-octyl-4-isothiazoline 3-o
5-chloro-2-methyl-4-isothiazoline 3-
On, 2- (4-thiazolyl) benzimidazole
You. Pyridine compounds are specifically 2,6-jumethylpi
Lysine, 2,4,6-trimethylpyridine, sodium-2-
Pyridinethiol-1-oxide and the like are preferred,
Or sodium-pyridinethiol-1-oxide.
You.   Guanidine compounds are specifically cyclohexidine,
Polyhexamethyleneguanidine hydrochloride, dodecylguani
Gin hydrochloride, preferably dodecylguanidine and
And its salts.   Carbamate compounds are specifically methyl-1- (butyl)
Chilkabamoyl) -2-benzimidazole kabame
And methylimidazole carbamate.   The morpholine compound is specifically 4- (2-nitrobutane).
Tyl) morpholine, 4- (3-nitrobutyl) morpholine
Etc.   The quaternary phosphonium compound is tetraalkylphosphoni
Salts, tetraalkoxyphosphonium salts, etc.
Preferably a tetraalkylphosphonium salt and further
A physically preferred compound is tri-n-butyl-tetradecyl
Phosphonium chloride, tri-phenyl nitrofe
There is nylphosphonium chloride.   The quaternary ammonium compound is specifically benzalkoniu
Salt, benzethonium salt, tetraalkylammonium
Salts and alkylbiridinium salts.
Dimethylbenzylammonium chloride, didecyl
Dimethyl ammonium chloride, lauryl pyridinium
Mucroid and the like.   The urea compound is specifically N- (3,4-dichlorophene).
Nyl) -N- (4-chlorophenyl) urea, N- (3-
Trifluoromethyl-4-chlorophenyl) -N- (4
-Chlorophenyl) urea and the like.   The isoxazole compound is specifically 3-hydroxy
-5-methyl-isoxazole and the like.   Propanolamine compounds are n-propanols
And isopropanols, specifically, DL-2-ben
Zylamino-1-propanol, 3-diethylamino-1
-Propanol, 2-dimethylamino-2-methyl-1
-Propanol, 3-amino-1-propanol, id
Propanolamine, diisopropanolamine, NN-
And dimethyl-isopropanolamine.   Sulfamide derivatives are specifically fluorinated sulfamides
, 4-chloro-3,5-dinitrobenzenesulfamido
Do, sulfanilamide, acetosulfamine, sulf
Apyridine, sulfaguanidine, sulfathiazo
, Sulfadiazine, sulfamerazine, sulfame
Tagine, sulfisoxazole, homosulfami
, Sulfisomidine, sulfaguanidine, sulfa
Methisol, sulfapyrazine, phthalisosulfati
Azole, succinylsulfathiazole and the like.   Amino acid compounds are specifically N-lauryl-β-a
There is lanin.   Amino acid compounds are specifically N-lauryl-β-a
There is lanin.   Benzotriazole compounds are specifically as follows
Is raised.   Among the above anti-binders, preferably used in the present invention.
Compounds used are phenolic compounds and thiazole compounds
Compounds, pyridine compounds, guanidine compounds, quaternary
Ammonium compounds and benzotriazole compounds
You. Furthermore, phenol is particularly preferable from the viewpoint of preserving the liquid.
-Based compounds, thiazole-based compounds and benzotriazole
It is a system compound.   The amount of the anti-bubble agent added to the washing stable liquid is
Less than 0.001g per liter of constant solution provides antifungal effect
In addition, if it is 50 g or more, it is not preferable in terms of cost,
Since the storage stability of the dye image deteriorates, 0.001 g to 50 g
g, preferably 0.005 g to 10 g.
Used.   Preferably used in the present invention among the above fungicides
Compounds are thiazole compounds and pyridine compounds
Substances, guanidine compounds and quaternary ammonium compounds
is there. Furthermore, thiazole compounds are particularly preferred.
You.   The amount of the fungicide to be added to the water washing alternative treatment solution depends on the water washing alternative treatment.
The range is preferably 0.002 g to 50 g per liter,
Preferably it is in the range of 0.005 g to 10 g.   Desirable to be added to the washing stable stabilizer used in the present invention
As a compound, it adjusts membrane surface pH and also has an effect on image preservation
Ammonium compounds having the following formulas:   These are due to ammonium salts of various inorganic and organic compounds.
But specifically, ammonium hydroxide, odor
Ammonium chloride, ammonium carbonate, ammonium chloride
System, ammonium hypophosphite, ammonium phosphate,
Ammonium phosphate, ammonium fluoride, acid fluoride
Ammonium, ammonium fluoroborate, arsenate
Monium, ammonium bicarbonate, ammonium hydrogen fluoride
, Ammonium hydrogen sulfate, ammonium sulfate, iodine
Ammonium fluoride, ammonium nitrate, ammonium pentaborate
Ammonium, ammonium acetate, ammonium adipate,
Ammonium urin tricarboxylate, ammonium benzoate
, Ammonium carbamate, ammonium citrate
Ammonium, diethyldithiocarbamate, ammonium formate
Ammonium, ammonium hydrogen malate, hydrogen oxalate
Ammonium, ammonium hydrogen phthalate, bitartrate
Ammonium, ammonium thiosulfate, ammonium sulfite
, Ammonium ethylenediaminetetraacetate, 1-hydrido
Roxyethylidene-1.1-ammonium diphosphonate,
Ammonium lactate, ammonium malate, maleic acid
Ammonium, ammonium oxalate, ammonium phthalate
, Ammonium bicitrate, pyrrolidine dithioca
Ammonium rubamate, ammonium salicylate,
Ammonium succinate, ammonium sulfanilate, sake
Ammonium citrate, 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
1 mol to 1.0 mol, preferably 0.002 to 0.2 mol.
Range of moles.   In the present invention, the washing alternative treatment solution is
Contains a chelating agent having a chelate stability constant of 8 or more
Preferably.   Here, the chelate stability constant is LG · Sill'en ·
A.E.Martell, “Stability Constants of Metal
−ion Complexes ", The Chemical Socity, London (196
4), by S. Chaberek and A.E.Martell, “Organic Sequeste
ring Agents ", Wiley (1959)
Means number.   Chelate stability constant for iron ion in the present invention
As a chelating agent having a carboxylic acid number of 8 or more,
Chelating agent, organic phosphoric acid chelating agent, inorganic phosphoric acid chelate
Agents, polyhydroxy compounds and the like. The above iron
On means ferric ion (Fe³⁺).   Chelate stability constant with ferric ion in the present invention
Examples of the compound of the chelating agent wherein is 8 or more include:
The following compounds are exemplified, but are not limited thereto.
There is no. That is, ethylenediamine diorthohydroxyfe
Nilacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid,
Hydroxyethyl ethylenediamine triacetic acid, dihydroxy
Siethyl glycine, ethylenediamine diacetate, ethylene
Diamine dipropionic acid, iminodiacetic acid, diethyleneto
Liamine pentaacetic acid, hydroxyethyl iminodiacetic acid, dia
Minopropanoltetraacetic acid, transcyclohexanedia
Mintetraacetic acid, ethylenediaminetetraacetic acid, glycol-A
Terdiaminetetraacetic acid, ethylenediaminetetrakismethi
Lenphosphonic acid, nitrilotrimethylenephosphonic acid, 1
-Hydroxyethylidene-1,1-diphosphonic acid, 1,1-di
Phosphonoethane-2-carboxylic acid, 2-phosphonobutane
-1,2,4-tricarboxylic acid, 1-hydroxy-1-phos
Honopropane-1,2,3-tricarboxylic acid, catechol-
3,5-disulfonic acid, sodium pyrophosphate, tetrapo
Sodium Liphosphate and Sodium Hexametaphosphate
And particularly preferably A-PO_ThreeM_Two(Where M is a hydrogen source
Atom, sodium atom, potassium atom, ammonium
Represents a cation. A represents an inorganic or organic substance. )
Compounds, for example, 2-phosphonobutane-1,2,4
-Tricarboxylic acid, 1,1-diphosphonoethane-2-cal
Boric acid, pyrophosphoric acid, sodium tetrapolyphosphate,
Sodium oxametaphosphate, sodium polyphosphate, d
Trilotrimethylene phosphonic acid, ethylenediamine tet
Laphosphonic acid, diethylenetriaminepentaphosphone
Acid, 1-hydroxypropylidene-1,1 diphosphonic acid,
1-aminoethylidene-1,1-diphosphonic acid, 1-hydrido
Roxyethylidene-1,1-diphosphonic acid and their salts
is there.   The amount of the chelating agent used in the present invention is
0.01 to 50 g, preferably 0.0
Good results are obtained in the range of 5 to 20 g.   The water-washing alternative treatment solution in the present invention is used together with the chelating agent.
It is preferable to contain a metal salt. Such metal salts
As, Ba, Ca, Ce, Co, In, La, Mn, Ni, Pb, Sn, Zn, Ti, Zr, M
g, A or Sr metal salt, halide, hydroxide,
Inorganic salts such as sulfates, carbonates, phosphates and acetates or water-soluble
It can be supplied as an active chelating agent. Stable liquid as used amount
1 × 10 per one^-Four~ 1 × 10^-1Molar range and preferred
Ha 4 x 10^-Four~ 2 × 10^-2More preferably 8 × 10^-Four~
1 × 10^-2Range of moles.   Other commonly known stabilizing bath additives include, for example,
For example, optical brighteners, surfactants, organic sulfur compounds, onium
Hardeners such as salt, formalin and chromium, various metal salts, etc.
However, the amount of these compounds added depends on the stability bath according to the present invention.
Is necessary to maintain the pH and when storing color photographic images
To the extent that it does not adversely affect stability and the occurrence of precipitation,
Whatever compound you use in any combination
I can't tell.   The processing temperature for the stabilization processing is preferably 15 ° C to 60 ° C.
Preferably, it is in the range of 20 ° C to 45 ° C.   The processing time is 2 minutes or less, and the effect of the present invention is within this range.
Appear more remarkably. More preferably, the processing time is 1
Minutes 30 seconds or less. On the other hand, if the processing time is too short,
The processing time should be at least 20 seconds because the effect of
Is desirable.   In the case of multiple tank stabilization processing, the processing time is shorter in the former tank
However, it is preferable that the processing time is longer in the later stage tank. Especially before
It is desirable to process sequentially with 20% to 50% additional processing time of the tank
New After the stabilization treatment according to the present invention, no water washing treatment is required.
Not necessary, but phosphorous
Water, formalin, surfactants, etc.
Surface cleaning etc. can be performed arbitrarily if necessary.
You.   In the stabilization process according to the present invention, the replacement
When the multi-layer counter current method is used,
It is preferable to supply to the bath and overflow from the previous bath
New   In the present invention, after the color development processing, the toner has fixing ability.
The processing solution having the fixing ability is determined.
In the case of liquid landing, a bleaching treatment is performed before that. The drift
Used in bleaching solution or bleach-fix solution used in whitening process
As the bleaching agent, a metal complex salt of an organic acid is used.
The metal complex salt oxidizes the metallic silver generated by the development to
At the same time as changing to silver halide, the uncolored part of the color former is colored.
It has the function of aminopolycarbohydrate
Acid, organic acid such as oxalic acid, citric acid, iron, cobalt,
Coordinated metal ions such as copper. Like this
Most preferred used to form metal complexes of mechanical acids
Organic acids include polycarboxylic acids and aminopolycarboxylic acids.
Rubonic acid. These polycarboxylic acids or
Aminopolycarboxylic acid is an alkali metal salt, ammonium
It may be a salt or a water-soluble amine salt.   The following are typical examples of these.
Can be [1] Ethylenediaminetetraacetic acid [2] diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)
−N, N ′, N′-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexadiaminetetraacetic acid [7] iminodiacetic acid [8] dihydroxyethylglycine citric acid (or
Tartaric acid) [9] Ethyl ether diamine tetraacetic acid [10] glycol etheramine tetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Tetraethylenediaminetetraacetate (trimethyl
Ruammonium) salt [15] tetrasodium ethylenediaminetetraacetate
salt [16] diethylenetriaminepentaacetic acid pentanatri
Um salt [17] Ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitrilotriacetic acid sodium salt [20] Sodium cyclohexanediaminetetraacetate
salt   The bleaching solution used is a metal complex salt of an organic acid as described above.
Contains various additives as well as bleach
Can be. Additives, especially alkali halides
Or ammonium halides, such as potassium bromide, bromide
Sodium, sodium chloride, ammonium bromide, etc.
May contain halogenating agents, metal salts, and chelating agents
desirable. Borate, oxalate, acetate, carbonate, phosphoric acid
PH buffers such as salts, alkylamines, polyethylene oxide
It is known to be added to normal bleaching liquids such as sides
Can be appropriately added.   Further, the fixing solution and the bleach-fixing solution may be ammonium sulfite.
, Potassium sulfite, sodium bisulfite, metabisulfite
Ammonium phosphate, potassium metabisulfite, metabisulfite
Sulfites such as sodium, boric acid, borax, sodium hydroxide
, Potassium hydroxide, sodium carbonate, potassium carbonate,
Sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate
PH buffer consisting of various salts such as ammonium and ammonium hydroxide
The agents can be used alone or in combination of two or more.   While adding the bleach-fix replenisher to the bleach-fix solution (bath),
When the bleach-fix solution (bath) is used, thiosulfate, thiosulfate
A cyanate or a sulfite may be contained.
Add these salts to the bleach-fix replenisher and add them to the processing bath.
May be supplemented.   In the present invention, the bleaching solution increases the activity of the bleach-fixing solution.
In the bleach-fix bath and in the bleach-fix replenisher storage tank
If necessary, blow air or oxygen.
May be used or a suitable oxidizing agent, such as peroxide
Hydrogen, bromate, persulfate and the like may be added as appropriate.   In the treatment method of the present invention, a water-washing alternative stabilizer is used.
Contains soluble silver complex salts such as lanthanum fixer and bleach-fixer
Silver may be recovered from the processing solution by a known method. For example, electricity
Decomposition method (French Patent No. 2,299,667), precipitation method (JP-A-52
−73037, German Patent No. 2,331,220), ion exchange method
(JP-A-51-17114, German Patent No. 2,548,237) and gold
Effective use of the genus replacement method (UK Patent No. 1,353,805)
it can.   In the processing method of the present invention, bleaching and
Stable after washing and fixing (or bleach-fixing)
Can be treated, washed with water, and then stabilized
May be. Hardening, neutralization, black and white development,
If necessary, known auxiliary processes such as reversal and small amount washing
It may be added. Representative examples of preferred processing methods
The following steps are included. (1) Color development → bleach-fix → stable (2) Color development → Bleaching and fixing → Washing with a small amount of water → Stable (3) Color development → Bleaching / fixing → Washing → Stable (4) Color development → bleach-fix → stable (5) Color development → Bleaching and fixing → First stable → Second stable (6) Color development → washing with water (or stable) → bleaching and fixing → stable (7) Color development → stop → bleach-fix → stable (8) Color development → bleaching → washing → fixing → washing → stable (9) Color development → Bleaching → Fixing → Rinsing → Stable (10) Color development → bleaching → washing with a small amount of water → fixing → first stabilization → first
2 stable (11) Color development → bleaching → washing with a small amount of water → fixing → washing with a small amount of water → water
Wash → stable (12) Color development → bleaching → fixing → stable (13) Color development → stop → bleach → small amount of water washing → fixing → small amount of water
Washing → water washing → stable   Silver halide color copying to which the processing method of the present invention is applied
Silver halide grains used in true light-sensitive materials include silver chloride
Can contain silver bromide and / or silver iodide.
Halogen consisting of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, etc.
Silver halide particles.   In the present invention, silver chlorobromide emulsion, especially high silver chloride emulsion
The effect on sensitometry is small when using
It is also suitable for rapid processing and has the effect of using the antioxidant of the present invention.
The fruits are noticeable. Specifically, in the present invention, silver chloride
The content is at least 70%, particularly preferably at least 90% by mole.
The above silver chlorobromide emulsion is preferred as the emulsion to which the present invention is applied.
No.   Crystals of silver halide grains used in the present invention are normal
Crystal, twin or other, {100} face and {111} face
Any ratio can be used. In addition, these halo
The crystal structure of silver gemide particles is uniform from inside to outside.
Even though the inside and outside are different layered structures (core and
(Well type). In addition, these c
Silverogenide is a type that forms a latent image mainly on the surface.
May also be of the type formed inside the particles. More flat
Silver halide grains (Japanese Patent Application Laid-Open No. 58-113934,
No. 170070) can also be used.   The silver halide grains used in the present invention are prepared by an acidic method,
It is obtained by any of the preparation methods,
Is also good.   Also, for example, seed particles are made by an acid method,
Grown by the fast ammonia method to a specified size
It may be a method of growing. Grow silver halide grains
Control the pH, pAg, etc. in the reaction vessel
For example, halogens described in JP-A-54-48521
Silver ions and halides in proportion to the growth rate of silver halide grains
It is preferable that ions are sequentially and simultaneously injected and mixed.   The preparation of silver halide grains according to the present invention is as described above.
It is preferable to carry out. Including the silver halide grains.
Having a silver halide emulsion as defined herein.
Say.   These silver halide emulsions contain active gelatin;
Sensitizers such as allylthiocarbamide, thiourea, cystine
Selenium sensitizers; reduction sensitizers such as No. 1
Tin salt, thiourea dioxide, polyamine, etc .; noble metal sensitizer
For example, gold sensitizers, specifically potassium aurithiocyane
, Potassium chloroaurate, 2-aurothio-3
-Methylbenzothiazolium chloride or the like
Ruthenium, palladium, platinum, rhodium, iridium
Sensitizers of water-soluble salts such as
Lopaladate, potassium chloroplatinate and nato
Lithium chloroparadate (some of these are
Acts as a sensitizer or fog inhibitor depending on the size
I do. ) Alone or in combination as appropriate (for example,
Sensitizer and sulfur sensitizer, gold sensitizer and selenium sensitizer
Combined use) and may be chemically sensitized.   The silver halide emulsion according to the present invention contains a sulfur-containing compound.
Add and chemically ripen, before this chemical ripening, during ripening, or
After aging, at least one type of hydroxytetrazaindene
Of nitrogen-containing heterocyclic compounds having
At least one kind may be contained.   The silver halide used in the present invention has a desired light sensitivity.
In order to impart photosensitivity to the wavelength range, an appropriate sensitizing dye is used.
5 × 10 for 1 mole of silver logenide^-3~ 3 × 10^-3Molar addition
Optical sensitization. Various sensitizing dyes
Can be used, and each sensitizing dye can be used alone or in combination.
It can be used in combination of more than one species. Yes in the present invention
Examples of sensitizing dyes that are advantageously used include the following:
Can be mentioned.   That is, sensitizing dyes used in blue-sensitive silver halide emulsions
As, for example, West German Patent 929,080, US Patent 2,231,6
No. 58, No. 2,493,748, No. 2,503,776, No. 2,519,001
Nos. 2,912,329, 3,656,959, 3,672,897,
No. 3,694,217, No. 4,025,349, No. 4,046,572, UK
Patent Nos. 1,242,588, JP-B-44-14030, JP-B-52-24844
And the like. Also green sensitivity
As sensitizing dyes used in silver halide emulsions, for example,
For example, British patents 1,939,201, 2,072,908, 2,733,149
No. 2,945,763, British Patent 505,979, etc.
Cyanine dye, merocyanine dye or complex
Anine dyes can be mentioned as typical examples.
You. In addition, sensitization used in red-sensitive silver halide emulsions
As the dyes, for example, U.S. Pat.Nos. 2,269,234 and 2,270,3
No. 78, No. 2,442,710, No. 2,454,629, No. 2,776,280
Cyani dyes, merocyanine dyes, etc.
Or citing complex cyanine dyes as typical ones
Can be Further, U.S. Pat.Nos. 2,213,995 and 2,4
Described in 93,748, 2,519,001, West German Patent 929,080, etc.
Cyanine dye, merocyanine dye or
Use complex cyanine dyes as green-sensitive silver halide emulsions or red-sensitive
Can be advantageously used for a neutral silver halide emulsion.   These sensitizing dyes may be used alone,
May be used in combination.   The photographic light-sensitive material of the present invention may contain cyanine or
Spectral sensitization method using a single or combination of Russianin dyes
Optical sensitization may be performed in a desired wavelength range.   Typical examples of particularly preferred spectral sensitization methods include:
For example, benzimidazolocarbocyanine and benzoxazo
JP-B-43-4936 concerning combination with locarbocyanine
No. 43-22884, No. 45-18433, No. 47-37443,
Nos. 48-28293, 49-6209, 53-12375, JP
52-23931, 52-51932, 54-80118, 58-1
No. 53926, No. 59-116646, No. 59-116647, etc.
Method.   Also, a carbocyanine having a benzimidazole nucleus and
Concerning combinations with other cyanines or merocyanines
As for example, JP-B-45-25831, JP-B-47-11114,
No. 47-25379, No. 48-38406, No. 48-38407, No. 54-3
No. 4535, No. 55-1569, JP-A No. 50-33220, No. 50-385
No. 26, No. 51-107127, No. 51-115820, No. 51-135528
Nos. 52-104916 and 52-104917.   In addition, benzoxazolocarbocyanine (oxa
Rubocyanin) and other carbocyanines
Examples thereof include JP-B-44-32753 and JP-B-46-11627.
No., JP-A-57-1483, relating to merocyanine
For example, Japanese Patent Publication Nos. 48-38408, 48-41204 and 50-
No. 40662, JP-A-56-25728, JP-A-58-10753, JP-A-58-9
No. 1445, No. 59-116645, No. 50-33828, etc.
You.   Also, a combination of thiacarbocyanine and another carbocyanine
For example, Japanese Patent Publication No. 434932/1972,
43-4933, 45-26470, 46-18107, 47-87
No. 41, JP-A-59-114533, etc.
Or dimethine merocyanine, monomethine or trimethine
JP-B-49-6207 using cyanine and styryl dye
Can be advantageously used.   These sensitizing dyes are used in the silver halide emulsion of the present invention.
For addition, for example, methyl alcohol
, Ethyl alcohol, acetone, dimethylforma
Mid or fluorinated alcohol described in JP-B-50-40659
It is used by dissolving it in a hydrophilic organic solvent such as toluene.   The timing of addition is at the beginning of the chemical ripening of the silver halide emulsion.
During ripening, it can be at any time at the end of ripening, and in some cases
It may be added to the step immediately before the emulsion coating.   The photographic coupler used in the present invention is
Phenol compounds, naphthol compounds
Compounds are preferred.   These cyan couplers are the same as the yellow couplers.
Not only equivalent couplers but also two equivalent couplers
Is also good. Specific examples of cyan couplers include U.S. Pat.
9,929, 2,434,272, 2,474,293, 2,521,908
Nos. 2,772,102, 2,895,826, 3,034,892
No. 3,311,476, No. 3,458,315, No. 3,476,563,
3,583,971, 3,591,383, 3,758,308, 3,7
67,411, 3,772,002, 3,933,393, 4,004,92
9, 4,126,396, 4,334,011, 4,327,173, West
German Patent Applications (OLS) 2,414,830, 2,454,329, 3,3
29,729, JP-A-48-59838, JP-A-51-26034, JP-A-48-59834
No. 5055, No. 51-146827, No. 52-69624, No. 52-90932
No. 58-95346, JP-B-49-11572, etc.
Can be mentioned.   Magenta couplers for photography include pyrazolone-based
Lazolotriazole, pyrazolinobenzimidazole
And indazolone-based compounds. Pyrazo
Ron-based magenta couplers include U.S. Pat.
Nos. 3,062,653, 3,127,269, 3,311,476,
3,419,391, 3,519,429, 3,558,318, 3,6
Nos. 84,514 and 3,888,680, JP-A-49-29639, and 39-
No. 111631, No. 49-129538, No. 50-13041, Tokiko Sho 53
-47167, 54-10491, 55-30615
Compound; pyrazolotriazole magenta coupler
-U.S. Patent No. 1,247,493, Belgian Patent 792,5
The coupler described in No. 25 is cited, and a diffusion-resistant colored
Colorless magenta is generally used for magenta couplers.
Arylazo substitution at the coupling position of ta coupler
Compounds are used, for example, U.S. Pat.
3,608, 3,005,712, 3,684,514, UK Patent 93
7,621, JP-A-49-123625 and JP-A-49-31448.
Compounds.   In addition, current conditions such as described in U.S. Pat.
The dye is flowing out of the processing solution due to the reaction with the oxidized form of the imaging agent.
Type of colored magenta coupler can also be used.
Wear.   As a yellow coupler for photography, open-chain keto
Methylene compounds are used and are widely used in general.
Benzoylacetanilide type yellow coupler,
Use pivaloylacetanilide type yellow coupler
be able to. Further, the carbon atom at the coupling position is
Substituted with a substituent capable of leaving during the ring reaction
Are also advantageously used.
You. Examples of these are U.S. Pat.Nos. 2,875,057 and 3,265,506.
No. 3,664,841, No. 3,408,194, No. 3,277,155,
3,447,928, 3,415,652, JP-B-49-13576,
JP-A-48-29432, JP-A-48-68834, JP-A-49-10736,
Nos. 49-122335, 50-28834, 50-132926, etc.
And the synthesis method.   The amount of the diffusion-resistant coupler used in the present invention is
Generally, 0.05 mol / mol of silver in the photosensitive silver halide emulsion layer is used.
~ 2.0 mol.   In the present invention, a DIR compound other than the above-described diffusion resistant coupler is used.
Is preferably used.   Furthermore, in addition to DIR compounds, development is suppressed with development.
Agent-releasing compounds are also included in the invention, e.g., U.S. Pat.
3,297,445, 3,379,529, West German Patent Application (OLS) 2,4
No. 17,914, JP-A-52-15271, JP-A-53-9116, and JP-A-59-1
Nos. 23838, 59-127038 and the like.
You.   The DIR compound used in the present invention is a color developing agent
Reacts with the oxidized form of the compound to release the development inhibitor
Compound.   A typical example of such a DIR compound is active
Forms a compound that has a development-inhibiting action when released from a point
A DIR cap in which a group that can be formed is introduced into the active site of the coupler.
There are, for example, British Patent 935,454, US Patent 3,22
7,554, 4,095,984, 4,149,886, etc.
ing.   The above DIR coupler is used for oxidizing the color developing agent
Upon the ring reaction, the coupler nucleus forms a dye,
On the other hand, it has the property of releasing a development inhibitor. Also in the present invention
Are U.S. Patent Nos. 3,652,234, 3,928,041, 3,958,993
No. 3,961,959, No. 4,052,213, JP-A-53-110529
Nos. 54-13333, 55-161237, etc.
Coupling reaction with the oxidized form of color developing agent
Compounds that release development inhibitors but do not form dyes
Things are also included.   Furthermore, JP-A-54-145135, JP-A-56-114946 and
Oxidation of color developing agent as described in JP-A-57-154234
When reacted with the body, the mother nucleus is a pigment or a colorless compound
, While the released timing group forms an intramolecular nucleophile.
Releases the development inhibitor by the exchange reaction or the elimination reaction
A so-called timing DIR compound which is a compound is also included in the present invention.
It is.   Also described in JP-A-58-160954 and JP-A-58-162949.
Completely reacts with the oxidized color developing agent
The above-mentioned tie
Includes timing DIR compounds to which the mining group is attached
Things.   The amount of the DIR compound contained in the photosensitive material is 1 mole of silver.
1 × 10^-FourMol to 10 × 10^-1Molar range is preferred
Can be.   Silver halide color photographic light-sensitive material used in the present invention
Can contain various other photographic additives.
You. For example, Research Disclosure Magazine No. 17643
Listed antifoggants, stabilizers, UV absorbers,
Color stain inhibitor, fluorescent whitening agent, color image fading inhibitor, antistatic
Uses stop agents, hardeners, surfactants, plasticizers, wetting agents, etc.
be able to.   Silver halide color photographic light-sensitive material used in the present invention
The hydrophilic roller used to prepare the emulsion
Id includes gelatin, derivative gelatin, gelatin and other
Graft polymer with polymer, albumin, kazenin
Etc., hydroxyethylcellulose derivatives, cal
Cellulose derivatives such as boxymethylcellulose, starch
Conductor, polyvinyl alcohol, polyvinyl imidazo
Of mono- or copolymers such as
Any one such as a synthetic hydrophilic polymer is included.   Silver halide color photographic light-sensitive material used in the present invention
Examples of the support include parita paper and polyethylene coating.
A covering paper, a polypropylene synthetic paper, and a reflective layer were provided. Or
Transparent support used in combination with a reflector, for example, a glass plate, cellulo
Acetate, cellulose nitrate or polyethylene
Polyester film such as lentephthalate, polya
Mid film, polycarbonate film, polystyrene
And other ordinary transparent supports.
You may. These supports are suitable for the intended use of the photosensitive material.
Selected as appropriate.   Silver halide emulsion layer used in the present invention and its
Taping coating, air
Various applications such as doctor application, curtain application, hopper application
A coating method can be used. U.S. Patent 2,761,79
Simultaneous two or more layers by the method described in No. 1, No. 2,941,398
A coating method can also be used.   In the present invention, the coating position of each emulsion layer is arbitrarily determined.
be able to. For example, for photosensitive materials for full-color photographic paper
In the case, a blue-sensitive silver halide emulsion is sequentially formed from the support side.
Layer, green photosensitive silver halide emulsion layer, red photosensitive halide
It is preferable to arrange the silver emulsion layer. These photosensitive
The silver halide emulsion layer may be composed of two or more layers.
Good.   In the light-sensitive material of the present invention, an appropriate thickness according to the purpose.
It is optional to provide an intermediate layer of
Layer, anti-curl layer, protective layer, anti-halation layer, etc.
Various layers can be used in appropriate combination as constituent layers
You. In these constituent layers, the emulsion as described above is used as a binder.
Use the same hydrophilic colloid that can be used for the layer
In the emulsion layer as described above.
Contains various photographic additives that can be used
Can be   Processing method of silver halide color photographic light-sensitive material of the present invention
In, as a silver halide color photographic light-sensitive material,
Processing is performed by the so-called internal development method in which the photosensitive material contains a coupler.
Color paper, color negative if the photosensitive material
Film, color positive film, color poly paper,
Color reversal film for slides, color reversal film for movies
LUM, color reversal film for TV, reversal color paper, etc.
Applicable to any silver halide color photographic material
Can be. [Specific effects of the invention]   As described above, according to the treatment method of the present invention, a toxic substance
Immediate storage stability instead of hydroxylamine
And no reduction in the maximum color density, and furthermore, photographic dye images
Silver halide color photographic exposure with excellent aging stability
The method of processing the material could be provided. 〔Example〕   Hereinafter, the present invention will be described specifically with reference to Examples.
Embodiments of the invention are not limited to these. Example 1   The following color developer was prepared. (Color developing solution)   Benzyl alcohol 15ml   Ethylene glycol 10ml   Potassium sulfite 4.0 × 10^-3Mole   Potassium bromide 1.0g   0.3 g sodium chloride   Potassium carbonate 25.0g   Preservative (listed in Table 1) 5.0g   Polyphosphoric acid (TPPS) 2.0g   5.0 g of color developing agent (Exemplified Compound A-1)   Optical brightener (4,4'-diaminostilbene) 2.0g   Potassium hydroxide and water were added to obtain 1. The pH is 1
It was set to 0.15.   5 ppm of ferric ion and 3 ppm of copper ion in the above color developing solution
And 100 ppm of calcium ion (each FeCl_Three, CuSO_Four・ 6H_Two
O and CaCl_TwoAt 50 ° C.
30cm^Two/ (1 developer has air contact area of 30c
m^Two) Was stored for one week in the glass container.   One week later, the appearance (coloring and tar) of the color developer
Observed.   However, the appearance of the liquid was evaluated in the following stages.       Large amount of tar generation       Blackening     + Browning (very discolored)     -Almost no discoloration   Table 1 shows the results.   As is clear from Table 1, the antioxidant of the present invention is used.
And color developer even if it contains iron and copper ions
Has good storage stability,
It has been improved to the same extent or better.   On the other hand, antioxidants outside the present invention have poor storage stability of the solution,
Obviously it can not be a substitute for hydroxylamine
Is. Reference example 2   The following layers are supported on a polyethylene-coated paper support
This was applied sequentially from the side to prepare a photosensitive material.   The average molecular weight of polyethylene coated paper is 10
200 parts by weight of polyethylene with a density of 0.90 and 0.95 and an average molecular weight
2,000, mixed with 20 parts by weight of polyethylene of density 0.80
6.8% by weight of anatase-type titanium oxide
170g / m weight by coating method^TwoHigh quality paper table
A 0.035 mm thick coating layer is formed on the
A coating layer with a thickness of 0.040 mm made only of styrene
Was used. The core is coated on the polyethylene-coated surface of the support.
After pre-treatment by Rona discharge, apply each layer sequentially
Was. First layer:   Blue sensitivity of silver halide emulsion of AgBr: AgCl = 70: 30
In the silver halide emulsion layer, the emulsion was equivalent to 1 mole of silver halide.
Containing 350 g of gelatin, per mole of silver halide
Structure sensitizing dye   2.5 × 10^-FourSensitized by using
Dissolves in dibutyl phthalate)
2,5-di-t-butylhydroquinone 200
mg / m^TwoAnd the following yellow coupler as a yellow coupler:
2 × 10 per mole of silver halide^-1Molar content, silver amount 300mg / m^TwoTo
It is applied so that it becomes. Second layer:   Di-t-oct dissolved and dispersed in dibutyl phthalate
Chill hydroquinone 300mg / m^Two, As an ultraviolet absorber
(2'-hydroxy-3 ', 5'-di-tert-butylphenyl)
B) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methyl
Phenyl) -5-chlorobenzotriazole and 2-
(2'-hydroxy-3 ', 5'-di-tert-butylphenyl)
L) -5-chloro-benzotriazole mixture 200 mg /
m^Two1900mg / m gelatin in the gelatin layer containing^TwoWill be
Is applied. Third tier:   Green sensitivity of silver halide emulsion of AgBr: AgCl = 70: 30
In a silver halide emulsion layer, the emulsion is 1 mole equivalent of silver halide.
Contains 450g of gelatin and lower per mole of silver halide
Sensitizing dye having the above structure   2.5 × 10^-FourMolar sensitized dibutyl phthalate
Solvent and tricresyl phosphate in a 2: 1 mixture
The following M-1 was used as a dissolved and dispersed magenta coupler.
1.5 × 10 per mol of silver genogenide^-1Molar content, silver amount 230
mg / m^TwoIt is applied so that it becomes. In addition, antioxidant
2,2,4-trimethyl-6-lauryloxy-7-
0.3 mol of t-octyl chroman per mol of coupler
Contained. Fourth layer:   Di-t-o dissolved and dispersed in dioctyl phthalate
Cutyl hydroquinone 30mg / m^TwoAnd as UV absorber
2- (2'-hydroxy-3 ', 5'-di-tert-butyl butyl
Enyl) benzotriazole, 2- (2'-hydroxy
-5'-t-butylphenyl) benzotriazole, 2
-(2'-hydroxy-3'-tert-butyl-5'-methyl
Ruphenyl) -5-chlorobenzotriazole and 2
-(2'-hydroxy-3 ', 5'-tert-butylphenyl
1) -5-chloro-benzotriazole mixture (2: 1.
5: 1.5: 2) 500mg / m^TwoContaining gelatin layer in gelatin
1900mg / m^TwoIt is applied so that it becomes. Fifth layer:   Red sensitivity consisting of silver halide emulsion of AgBr: AgCl = 50: 50
In a silver halide emulsion layer, the emulsion is 1 mole equivalent of silver halide.
Contains 500 g of gelatin and lower per mole of silver halide
Sensitizing dye having the above structure   2.5 × 10^-FiveMolar sensitized dibutyl phthalate
2,5-di-t-butylhydrogen dissolved and dispersed in
Quinone 150mg / m^TwoAnd the following cyan coupler C′-1
3.5 × 10 per mol of silver genide^-1Molar content, silver amount 280mg
/ m^TwoIt is applied so that it becomes. Sixth layer:   900mg / m gelatin in gelatin layer^TwoApply so that
Have been.   Halogen used in each of the above photosensitive emulsion layers (first, third, and fifth layers)
The silver halide emulsion is prepared by the method described in JP-B-46-7772.
With sodium thiosulfate pentahydrate
Sensitized with 4-hydroxy-6-methyl
1,3,3a, 7-tetrazaindene, bis as a hardener
(Vinylsulfonylmethyl) ether and coating aid
To contain saponin. (Compounds used in Examples)   Stepwise exposing the color paper sample thus produced,
It processed by the following processing steps. Processing steps (1) Color development 38 ° C 3 minutes 30 seconds (2) Bleaching and fixing 33 ° C for 1 minute and 30 seconds (3) Rinse with water (pool water) 30 ℃ 30 seconds (4) Treatment or washing with running stabilizer instead of water (running water)                     30 ℃ 1 minute 0 seconds   The composition of the processing solution used is as follows. (Color developing solution)   Benzyl alcohol 15ml   Ethylene glycol 10ml   Potassium sulfite 1.0 × 10^-2Mole   5.0 g of color developing agent (A-1)   Antioxidant (listed in Table 2) 10.0g   Triethanolamine 10.0g   Potassium carbonate 30g   Sodium ethylenediaminetetraacetate 2.0g   Optical brightener (4,4'-diaminostilbene disulfone
Acid derivative) 2.0g   Finish to 1 with water, pH 10.15 with potassium hydroxide or sulfuric acid
Was adjusted. (Bleach-fix tank liquid)   Ferric ammonium ethylenediaminetetraacetate diwater
60.0g salt   3.0 g of ethylenediaminetetraacetic acid   Ammonium thiosulfate (70% solution) 100.0ml   Ammonium sulfite (40% solution) 27.5ml   Adjust to pH 5.50 with ammonium water or glacial acetic acid. (Washing substitute stabilizer)   EDTAFe (III) NH_Three・ 2H_TwoO aqueous solution   (Concentration is as shown in Table 2), pH 7.5   After squeezing the sample after the process of (4), drying
And the maximum color density of cyan dye (reflection density)
Measured with A-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.)
After leaving for 14 days at 75 ° C and 60% relative humidity,
Measure the maximum color density of the cyan dye again, and
Density change (ΔD_R) Were obtained and are shown in Table 2.   As is clear from the results shown in Table 2, the color developing solution
When using the antioxidant of the invention, washing with water and soluble iron salt
2.0 × 10 density^-FiveIn the alternative stabilization treatment of mol /
The change in the maximum color density of cyan dye is large, but soluble iron
Salt concentration 2.0 × 10^-FourAbove mol, cyan dye fading is extremely
Not much.   The soluble iron salt concentration was 5 × 10^-2In mole /
Yellow stain increased significantly. Example 3   The silver halide emulsion of the light-sensitive material used in Reference Example 2 was AgB
r: AgCl = 4: 96 high temperature silver emulsion (photosensitive material 1), AgBr: AgC
l = 25: 75 emulsion (photosensitive material 2) and AgBr: AgCl = 35: 76
Photosensitive material of Reference Example 2 except that emulsion (photosensitive material 3) was used
Created in the same way as   Color paper samples (No.14 to No.3)
7) After printing, print automatically according to the following processing steps.
Running processing was performed by the image machine. Processing steps (1) Color development 35 ° C 45 seconds (2) Bleaching and fixing 35 ° C 45 seconds (3) Rinse-wash alternative 30 ° C 90 seconds (4) Drying 60 ° C-80 ° C 1 minute 30 seconds   The composition of the processing solution used is as follows. (Color developing tank liquid)   Potassium chloride 2.0g   Potassium sulfite 6.5 × 10^-3Mole   5.0 g of color developing agent (A-1)   Antioxidants (listed in Table 3) 5.0g   Triethanolamine 10.0g   Potassium carbonate 30g   Sodium ethylenediaminetetraacetate 2.0g   Optical brightener (4,4-diaminostilbene disulfonic acid
Derivative) 2.0g   Finish to 1 with water, pH 10.15 with potassium hydroxide or sulfuric acid
Was adjusted. (Color development replenisher)   2.5 g potassium chloride   Potassium sulfite (50% solution) 7.0 × 10^-3Mole   8.0 g of color developing agent (A-1)   Antioxidants (listed in Table 3) 7.0g   Triethanolamine 10.0g   Potassium carbonate 30g   Sodium ethylenediaminetetraacetate 2.0g   Add water to finish to 1 and add potassium hydroxide or sulfuric acid
The pH was adjusted to 10.40. (Bleach-fix tank liquid)   Ferric ammonium ethylenediaminetetraacetate diwater
60.0g salt   3.0 g of ethylenediaminetetraacetic acid   Ammonium thiosulfate (70% solution) 100.0ml   Ammonium sulfite (40% solution) 27.5ml   Adjust to pH 5.50 with ammonium water or glacial acetic acid
Water to make the total amount 1. (Bleach-fix replenisher)   Ferric ammonium ethylenediaminetetraacetate diwater
70.0g salt   3.0 g of ethylenediaminetetraacetic acid   Ammonium thiosulfate (70% solution) 120.0ml   Ammonium sulfite (40% solution) 35ml   Adjust the pH to 5.40 with ammonium water or glacial acetic acid,
Let it be 1. (Washing substitute stable tank solution and replenisher)   Orthophenylphenol 0.2g   1-hydroxyethylidene-1,1-diphosphonic acid (60
% Aqueous solution) 2.0g   Ammonium water 3.0g   Adjust to 1 with water and adjust to pH 7.8 with ammonium water or sulfuric acid
It was adjusted.   Running process is nice print system RP-500
(Using Konishi Roku Kogyo Co., Ltd.)
Color developing tank solution, bleach-fixing tank solution and water washing alternative
Fill the constant tank liquid and do not process the color paper sample.
Color development replenisher, bleach-fix replenisher and washing allowance
While replenishing the replacement stable replenisher through the metering pump.
Was. Replenishment amount is 1m of color paper^TwoTo the color development tank
220ml replenishment rate, 220ml replenishment rate to bleach-fix tank, stable
Table 3 shows the amount of replenishment to the tank.   Note that the stabilization tank of the automatic developing machine
The first tank to the third tank will be a stable tank, and replenishment will be performed from the last tank.
The overflow liquid from the last tank to the previous tank.
And then add the overflow solution to the previous stage again.
A multi-tank countercurrent system was used to flow into the tank. However, front tank bleaching
The amount brought in from the fixing tank is 50 ml / m^TwoMet.   The above color paper sample is replenished with the color developer.
Run the running process until the color developing tank is replenished three times.
After that, the maximum emission of cyan
The color reflection density was measured using the PDA-65. Then 75
Leave for 30 days at 69 ° C and 69% RH, and the maximum emission of cyan dye
Change in color density (△ D_R) Was measured. Table 3 shows the results.   Also, at this time, the third tank of the alternative washing bath (final
Tank) was analyzed by atomic absorption spectrometry, and the results were
It is shown in Table 3.   As is clear from the results in Table 3, the antioxidant of the present invention
By performing under the processing conditions of the present invention,
It is significantly prevented. No. 14 to No. 16 and No. 2
In No. 2 to No. 24 and No. 30 to No. 32, No. 14 hydro
Xylamine sulfate has a remarkably low coloring density, followed by No. 2
2, the color density decreases in the order of No. 30, for example, No. 14
The antioxidant of the invention has a concentration of about 1/2,
Roxyurea was about 2/3. No.16 glucose tank
Tar had adhered to the wall of.   Comparison of photosensitive materials 1, 2 and 3 shows that silver chloride
The higher the content, the more cyan it is, especially when the salt is 90 mol% or more
Change in the maximum color density of the element (ΔD_R) Is smaller
I understand.

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Yoko Matsushima               1 Sakuracho, Hino City Konishi Roku Photo Industry               Inside the corporation                    Panel     Referee Takehiko Takahashi     Referee Ichino     Judge Tetsuo Taki                (56) References JP-A-61-141447 (JP, A)                 JP-A-61-39046 (JP, A)                 JP-A-58-14834 (JP, A)                 JP-A-61-35446 (JP, A)                 Tokuyo Sho 63-502222 (JP, A)

Claims (1)

(57) [Claims] A silver halide color photographic light-sensitive material containing at least one silver halide emulsion layer having a silver chloride content of 70 mol% or more is color-developed with a color developer containing a hydroxylamine represented by the following general formula [I]. After processing with a processing solution having a fixing ability, 1 × 10 ^-4 or more and 1 × 10
^-2 mol or less of a soluble iron salt is treated with a water-washing alternative stabilizing solution, and the replenishment amount of the water-washing alternative stabilizing solution is 2 to 20 times the carry-in amount from the previous bath per unit area of the photosensitive material to be processed. , 250 ml / m ² or less, a method for processing a silver halide color photographic light-sensitive material. General formula [I] [Wherein, R ¹ and R ² each represent a hydrogen atom or an alkyl group which may have a substituent. However, R ¹ and R ² are not hydrogen atoms at the same time, and exclude the case of a methoxy group as a substituent for the alkyl group. However, this excludes the case where a compound of the following general formula [A] is used in combination with a color developing solution. General formula [A] [In the formula of the general formula [A], R ³ and R ⁴ represent a hydroxyalkyl group having 2 to 6 carbon atoms, and R ⁵ represents a substituted alkyl group having 1 to 6 carbon atoms. ]