JP3230881B2 - Stabilizing processing solution for silver halide color photographic light-sensitive material and processing method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilizing processing solution used for processing a silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as "photosensitive material") and a processing method using the same. is there.

[0002]

2. Description of the Related Art Generally, the basic steps of processing a silver halide color photographic light-sensitive material are a color development step and a desilvering step.
In the color developing step, the silver halide exposed by the color developing agent is reduced to form silver, and the oxidized color developing agent reacts with a color forming agent (coupler) to give a dye image. In general, a silver halide color photographic light-sensitive material undergoes a color development step after imagewise exposure, whereas a silver halide color reversal photographic light-sensitive material develops a color after imagewise exposure, followed by black-and-white development and a reversal step. A development step is performed. In the subsequent desilvering step, silver produced in the color developing step is oxidized by the action of an oxidizing agent commonly called a bleaching agent, and then dissolved by a silver ion complex ion forming agent commonly called a fixing agent. You. Through this desilvering step, only a dye image is formed on the color photographic material. The desilvering step thus generally comprises a bleaching step and a fixing step. Here, when the bleaching step and the fixing step are a bleach-fixing step performed in one bath, the bleach-fixing step may be performed after the bleaching step, or the bleach-fixing step may be performed between the bleaching step and the fixing step.

The photosensitive material on which a dye image has been formed is processed with a stabilizing solution after desilvering in order to preserve the obtained dye image. The treatment with the stabilizing solution is carried out after the washing step or directly after the desilvering treatment. In the processing of a color reversal photosensitive material, there is also known a method of stabilizing a dye image by adding an image stabilizer to an adjusting solution instead of using a stabilizing solution of a final bath. The stabilizing solution contains various compounds for improving the stability of the stabilizing solution itself, in addition to the image stabilizer for stabilizing the dye image of the photosensitive material. For example, U.S. Pat.No. 3,140,177 describes stabilizing an image using a stabilizing solution containing a polybasic organic acid such as citric acid or succinic acid. When the processing is performed, there is a problem that dirt frequently adheres to the photosensitive material, and there is a problem that these stable replenishers form precipitates in the solution over time.

[0004]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a stabilized treating solution which prevents the generation of precipitates in the solution with the passage of time and a treating method using the same. . A second object of the present invention is to provide a stabilized processing solution which prevents the adhesion of dirt to a photosensitive material in continuous processing, and a processing method using the same. A third object is to provide a stabilized processing solution having excellent image stability and a processing method using the same.

[Means for Solving the Problems] As a result of studying the above problems, the present inventor has found that the object can be achieved by the following stabilizing solution and a processing method using the same. . That is, (1) at least
At least one monobasic organic acid having one hydroxy group
One type, (a) hydroxybenzaldehydes, b)
Xamethylenetetramine, (c) N-methylolazo
(D) azolylmethylamines, (e) heterogen
Azoles in which the child is composed of only nitrogen atoms, (f)
Xycarbonylaldehyde and (g) pyridylaldehyde
Containing at least one compound selected from the group consisting of
Stabilizing solution for silver halide color photographic materials.

Hereinafter, the present invention will be described in detail. The stabilizing processing solution of the present invention refers to a processing solution having an effect of stabilizing a dye image formed by color development (particularly, an effect of preventing fading of a magenta dye over time), and includes a replenisher. It is. Preferred are processing solutions used after color development, preferably stabilizing solutions and adjusting solutions, and particularly preferred are stabilizing solutions. The compounds of the present invention
It may be added to the replenisher in each step, which is a preferred embodiment of the present invention. The replenisher in the present invention is a replenisher that is replenished to maintain the composition of the replenisher during continuous processing. The stabilizing solution in the present invention is a stabilizing solution or a stabilizing solution alternative to water washing conventionally used in a final processing step of a color negative film or a color reversal film. It also includes a stabilizer used in the final step, but is preferably used in the final step.

Hydroxides contained in the stabilizing solution of the present invention
The monobasic organic acid having a digroup will be described in detail below. The monobasic organic acid having a hydroxy group of the present invention,
Linear or branched having a hydroxy group site and a basic acid site
Consists of an alkyl group. There are no 2 carbon atoms in the compound
6 is preferable, and 2 to 4 are more preferable.
New Organic acid sites include carboxylic acids, sulfonic acids,
Acids are preferred, especially carboxylic acids. That is, below
Those represented by the general formula (I) are preferred. General formula (I) HO-L-COOH L is to table <br/> Wa a linear or branched alkyl group having 1 to 5 carbon atoms. In the following, specific examples of the compound represented by the general formula (I) according to the present invention are shown below, but the invention is not limited thereto.

[0008]

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Of the above organic acids, 1-1 and 1-2 are preferable, and 1-1 is particularly preferable. The content of these organic acids is 0.001 per liter of the stabilizing solution.
001 to 0.5 mol is preferable, and 0.0001 to 0.1
Mole is more preferred.

The stabilizing solution of the present invention contains a compound for stabilizing a dye image (hereinafter referred to as an image stabilizer), for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylene Tetramine and its derivatives, hexahydrotriazine and its derivatives, dimethylol urea,
An N-methylol compound such as N-methylolpyrazole can be added. In the present invention, when the concentration of free formaldehyde in the liquid is 0 to 0.01%,
Further, when the content is 0 to 0.005%, the effect is large and preferable. Examples of image stabilizers for achieving such a free formaldehyde concentration include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, and N, N'-bis. JP-A-4-3137 such as (1,2,4-triazol-1-ylmethyl) piperazine
Azolylmethylamines described in No. 53 are preferred. In particular, JP-A-4-359249 (corresponding to European Patent Publication No. 51)
No. 9190A2) and azolylmethylamine such as 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine and derivatives thereof in combination with azoles such as 1,2,4-triazole. Are particularly preferred. Up
Among the preferred image stabilizers described above, particularly preferred compounds
The products include (a) hydroxybenzaldehydes,
b) hexamethylenetetramine, (c) N-methylol
Azoles, (d) azolylmethylamines, (e)
Azoles in which the terrorist atom is composed only of a nitrogen atom,
(F) methoxycarbonyl aldehyde and (g) pyridi
And (a) the aldehyde described above in the present invention.
Droxybenzaldehydes are substituted at the hydroxy group
Any of the o-, m- and p-positions relative to the aldehyde group
And the benzene ring has 1 to 3 carbon atoms
Replacement linear or branched alkyl group, hydroxyalkyl group
Or an alkoxy group may be substituted, and further oxolane
Hydroxybenz in which a ring or a dioxane ring may be condensed
Aldehyde. (C) N-methylolazo
Are straight-chain or unsubstituted C 1 -C 3
Is a branched alkyl group, hydroxyalkyl group or alcohol
N-methylolazole which may be substituted with a xy group
You. (D) Azolylmethylamines have a carbon atom on the azole ring.
An unsubstituted linear or branched alkyl group having 1 to 3 primes,
The hydroxy group or the alkoxy group may be substituted.
And the amino nitrogen atom has a straight or branched chain having 1 to 3 carbon atoms.
Is substituted with an unsubstituted alkyl or hydroxyalkyl group.
And two molecules of azolylmethylamine
Unsubstituted straight-chain alkylene having 1 to 3 carbon atoms
Bis or two molecules of azolylmethylamine linked by a group
Is a bond in which amino nitrogens form a morpholine ring
Azolylmethylamine which may be in the form of
(E) an azole in which a hetero atom is constituted only by a nitrogen atom
Are unsubstituted straight-chain or 1 to 3 carbon atoms in the azole ring;
A branched alkyl or alkoxy group may be substituted.

[0011]

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[0012]

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A-23 Hexamethylenetetramine A-24 N-methylolurea

The content of these image stabilizers is
The amount is preferably 0.001 to 0.1 mol, more preferably 0.001 to 0.05 mol, per liter of the stabilization treatment liquid.

The stabilizer of the present invention preferably contains various surfactants in order to prevent unevenness of water droplets when the processed photographic material is dried. As such a surfactant, a polyethylene glycol type nonionic surfactant,
Polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant, alkylnaphthalene sulfonate type anionic surfactant, quaternary ammonium salt It is preferable to use a nonionic surfactant, for example, a cationic surfactant of an amine type, a cationic surfactant of an amine salt type, an amphoteric surfactant of an amino salt type, and a betaine-type amphoteric surfactant. Nonionic surfactants of alkylphenoxypolyethylene oxides and alkylphenoxypolyhydroxypropylene oxides represented by W) are preferred.

[0016]

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(Where W is -CH_TwoCH_TwoO- or -CH_TwoCH (O
H) CH_TwoO-₁And R_TwoIs alkyl
And n represents 0 or 1. m is -CH_TwoCH_TwoO-
Or -CH _TwoCH (OH) CH_TwoIndicates the number of moles of added O-. ) R₁
And R_TwoThe alkyl group of 3 to 20 carbon atoms is preferable.
Or C6-C12, especially octyl, nonyl, dodecy
And m as the number of moles added is particularly preferably 6 to 1
4 is preferred. Especially when the free formaldehyde concentration is low
If W is -CH_TwoCH (OH) CH_TwoPreferably O-
No. Examples of preferred surfactants are shown below, but the present invention
It is not limited to this.

[0018]

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It is also preferable to use a silicon surfactant having a high defoaming effect. The addition amount of the surfactant is 0.005 g to 3 g, preferably 0.02 to 0.3 g, per liter of the stabilizing solution. If necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, alkanolamines described in U.S. Pat. It is also preferable to include the sulfinic acid compound described in JP 231051A.

The stabilizing solution of the present invention may contain various chelating agents to improve the stability of the stabilizing solution,
It can be used preferably for reducing the generation of dirt. Preferred chelating agents include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Particularly preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N,
Organic phosphonic acids such as N'-trimethylene phosphonic acid, diethylenetriamine-N, N, N ', N'-tetramethylene phosphonic acid, or EP 345,172
The hydrolyzate of the maleic anhydride polymer described in A1 can be used. The preferable addition amount of these chelating agents is 0.000 per liter of the stabilizing solution.
It is from 0.01 to 0.01 mol.

The stabilizing solution of the present invention preferably contains an antibacterial / antifungal agent for the purpose of preventing the generation of bacteria and fungi, and commercially available products can be used. These antibacterial
Examples of fungicides include thiazolyl benzimidazole compounds as disclosed in JP-A-57-157244 and JP-A-58-105145, isothiazolone-based compounds as disclosed in JP-A-57-8542, and trichloro. Chlorophenol compounds represented by phenol,
Bromophenol compounds, organotin and organozinc compounds, acid amide compounds, diazines and triazine compounds, thiourea compounds, benzotriazole compounds,
Alkylguanidine compounds, quaternary ammonium salts represented by benzalkonium chloride, penicillins, antibiotics represented by aminoglycosides, and the like, Journal Antibacterial and Antifangus Agent (J. Antibact. Antifung.
Agents) Vol 1. No.5, p. 207-223 (198
The general-purpose anti-blur agent described in 3) is exemplified. Also, various disinfectants described in JP-A-48-83820, chlorine disinfectants such as chlorinated sodium isocyanurate, etc., Hiroshi Horiguchi, "Chemistry of Fungicides and Fungicides" (1986) Sankyo Publishing, Sanitary Technology "Sterilization, disinfection, and fungicide technology of microorganisms" (1982), Technical Association of Japan
) Can also be used. These are 2
More than one species may be used in combination. Examples of preservatives and antibacterial agents in the stabilizing solution of the present invention include those described in The Merck Index, 11th Edition (1989), Merk & Co. , INC.
The aminoglycosides described are preferred, and among the aminoglycosides, gentamicins are particularly preferred. Particularly, in a stabilized processing solution having a low free formaldehyde concentration as described above, the generated suspended matter is prevented from adhering to the photosensitive material. The preferable addition amount of these antibacterial and antifungal agents is 0.001 to 1 g per liter of the stabilizing solution, and more preferably 0.005 to 0.5 g.

In the present invention, after the desilvering treatment, a treatment with a stabilizing solution may be carried out after a washing treatment, or a treatment with a stabilizing solution may be carried out directly without a washing treatment.
The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in Jour
n-al of the Society of Motion Picture and Televis
ion Engineers Vol. 64, pp. 248-253 (May 1955)
Can be obtained by the method described in (1). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the treatment of the present invention, as a solution to such a problem, the method for reducing calcium ions and magnesium ions described in JP-A-62-288,838 can be used very effectively. Also, JP-A-57-8,5
No. 42, isothiazolone compounds and thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Sanitary Technology Association, "Sterilization, disinfection, and fungicide technology for microorganisms" (1982) Use of the fungicide described in the Industrial Technology Association, "Encyclopedia of Fungicides and Fungicides" (ed. 1986) Is preferred.

The pH of the stabilizer and washing water of the present invention is 4 to 9
And preferably 5 to 8. The processing temperature and the processing time can also be variously set depending on the characteristics of the light-sensitive material, the application, and the like, but are generally 20 seconds to 10 minutes at 15 to 45 ° C, and preferably 30 to 40 minutes at 25 to 40 ° C.
Seconds to 2 minutes. Further, when the stabilizer of the present invention is treated directly with the stabilizer after desilvering without washing with water, the effect of preventing contamination is remarkably exhibited. The treatment with the stabilizer of the present invention is described in JP-A-57-8543, JP-A-58-14834,
All known methods described in JP-A-60-220345 can be used. The replenishing amount of the stabilizer of the present invention is preferably 200 to 2000 ml per 1 m ² of the light-sensitive material. Washing with water and / or
Alternatively, the overflow solution accompanying the replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

According to the present invention, except for the stabilizing treatment solution, Research Disclosure Magazine No. 17643, pp. 28-29,
No. 18716, 651 left column to right column, and No. 307105
The development can be carried out by the usual method described on pages 880 to 881. The color developing solution used in the development processing of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent,
P-phenylenediamine compounds are preferably used, and as typical examples, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-
β-methanesulfonamidoethylaniline, 3-methyl-4-
Amino-N-ethyl-β-methoxyethylaniline, 4-
Amino-3-methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl- N-
Ethyl-N- (2-hydroxypropyl) aniline, 4-amino
-3-Ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N -Methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-
Methyl-N-methyl-N- (4-hydroxybutyl) aniline,
4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-
Hydroxybutyl) aniline, 4-amino-3-ethyl-N-
Ethyl-N- (3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-methyl-N- (5-
(Hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, N-bis ( Five
-Hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, in particular, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 4-amino
-3-Methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluene Sulfonates or sulfates are preferred. These compounds can be used in combination of two or more depending on the purpose.

The amount of the aromatic primary amine developing agent used is preferably 0.0002 mol to 0.2 mol, more preferably 0.001 mol to 0.1 mol per liter of the color developing solution.
1 mole.

The color developing solution comprises a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor or an antifoggant such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. If necessary, hydroxylamine, diethylhydroxylamine, hydroxylamine represented by the general formula (I) of JP-A-3-144446, sulfite, N,
Hydrazines such as N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, Development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos Various chelating agents such as carboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphone , Nitrilo -N, N, N-
Trimethylenephosphonic acid, ethylenediamine-N, N, N, N-
Tetramethylenephosphonic acid, ethylenediamine-di (o
-Hydroxyphenylacetic acid) and salts thereof. The processing temperature of the color developing solution in the invention is from 20 to 55C, preferably from 30 to 55C. Processing time is 20 seconds to 5 minutes for the photographic material,
Preferably it is 30 seconds to 3 minutes and 20 seconds. More preferably, the time is from 1 minute to 2 minutes and 30 seconds.
0 second to 1 minute 20 seconds, preferably 10 seconds to 60 seconds,
More preferably, it is 10 to 40 seconds.

When the reversal process is performed, color development is usually performed after black and white development. Known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone in the black-and-white developer. Alternatively, they can be used in combination. The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between processing solution and air (cm ² )] ÷
[Capacity of treatment liquid (cm ³ )] The above opening ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank,
Examples thereof include a method using a movable lid described in JP-A-1-82033 and a slit developing method described in JP-A-63-216050. Reducing the aperture ratio is not only in both the color development and black-and-white development steps, but also in the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol etherdiaminetetraacetic acid,
Bleaching agents such as iron complex salts of 1,3-propylenediaminetetraacetate from the lower right column of the fourth page to the upper left column of the fifth page; carbamoyl-based bleaching agents described in JP-A-4-73647; Bleaching agents, bleaching agents having a heterocyclic ring described in JP-A-4-174432, bleaching agents described in European Patent Publication No. 520457, including N- (2-carboxyphenyl) iminodiacetic acid ferric complex salt; Japanese Patent Application No. 3-252775 including ferric acetic acid ethylenediamine-N-2-carboxyphenyl-N, N ', N'-triacetate
A bleaching agent described in EP-A-501479, a bleaching agent described in JP-A-4-127145,
Ferric aminopolycarboxylic acid salts described in page (11) of JP-A-3-144446 or salts thereof are preferably used. The iron (III) complex salt of an organic aminocarboxylic acid is particularly useful in a bleaching solution and a bleach-fixing solution.
The pH of the bleaching solution or the bleach-fixing solution using these organic aminocarboxylic acid iron (III) complex salts is usually from 4.0 to 8, but the processing can be carried out at a lower pH to speed up the processing.

These bleaching treatments are preferably carried out immediately after color development, but in the case of reversal treatments, they are generally carried out via an adjusting bath (a bleaching accelerating bath may be used). When the above-mentioned image stabilizer is used as a stabilizing treatment solution in these adjusting baths (adjusting stabilizing solution), it is preferable to use the organic acid of the present invention in combination, because image stability is improved. As the adjusting solution, in addition to the image stabilizer and the organic acid of the present invention, aminopolycarboxylic acid chelating agents such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, and cyclohexanediaminetetraacetic acid; Sodium sulfite, sulfites such as ammonium sulfite and thioglycerin, aminoethanethiol,
Various bleaching accelerators described below such as sulfoethanethiol can be contained. For the purpose of preventing scum, sorbitan esters of ethylene oxide-substituted fatty acids described in U.S. Pat. No. 4,839,262, U.S. Pat. No. 4,059,446 and Research Disclosure, Vol. It is preferable to contain the described polyoxyethylene compound or the like. These compounds are used in an amount of 0.1
Although it can be used in the range of g to 20 g, it is preferably in the range of 1 g to 5 g. The pH of the conditioning bath is usually 3 to
It is used in the range of 11, preferably 4 to 9, and more preferably 4.5 to 7. The processing time in the conditioning bath is 2
It is preferably 0 seconds to 5 minutes. More preferably 20
Seconds to 100 seconds, most preferably 20 seconds to 60 seconds. The replenishing amount of the conditioning bath is preferably 30 ml to 3000 ml per 1 m ² of the light-sensitive material, and particularly preferably 50 ml to 150 ml.
It is preferably 0 ml. The processing temperature of the conditioning bath is 20 ° C
The temperature is preferably from 50 to 50 ° C, particularly preferably from 30 to 40 ° C.

In the present invention, in addition to the bleaching agent, the desilvering bath contains a rehalogenating agent, a pH buffering agent and a known additive described on page (12) of JP-A-3-144446. Carboxylic acids, organic phosphonic acids and the like can be used. In the present invention, various bleaching accelerators can be added to the bleaching solution or its pre-bath. Such bleach accelerators are described, for example, in U.S. Pat.
893,858, German Patent 1,290,8
21, compounds having a mercapto group or a disulfide group described in British Patent No. 1,138,842, JP-A-53-95630, and Research Disclosure No. 17129 (July 1978). Thiazolidine derivatives described in JP-A-50-140129, thiourea derivatives described in U.S. Pat. No. 3,706,561, iodides described in JP-A-58-16235, German Patent 2,748,430, polyethylene oxides described in JP-B-45-430.
For example, a polyamine compound described in JP-A-8836 can be used. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. Particularly preferred are British Patent No. 1,138,842,
Mercapto compounds as described in -190856 are preferred. In the bleaching solution and the bleach-fixing solution, in addition to the above compounds,
It is preferable to contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids have an acid dissociation constant (pKa)
Is 2 to 5, and specifically, acetic acid, propionic acid, hydroxyacetic acid and the like are preferable.

The light-sensitive material processed with a processing solution having a bleaching ability is subjected to fixing or bleach-fixing processing. As such a fixing solution or a bleach-fixing solution, those described in JP-A-3-33847, page 6, lower right column, line 16 to page 8, upper left column, line 15 are preferable. As a fixing agent in the desilvering step, ammonium thiosulfate has been generally used, but other known fixing agents, for example, mesoionic compounds,
It may be replaced with a thioether compound, thioureas, a large amount of iodide, hypo or the like. These are described in JP-A-60-61749, JP-A-60-147735, and JP-A-60-147735.
-21444, JP-A-1-201659, 1-2
Nos. 10951 and 2-44355, U.S. Pat.
No. 78,424 and the like. For example, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, ammonium thiocyanate,
Sodium thiocyanate, potassium thiocyanate, dihydroxyethyl-thioether, 3,6-dithia-1,
8-octanediol, imidazole and the like.
Of these, thiosulfates and mesoions are preferred. Ammonium thiosulfate is preferred from the viewpoint of quick fixability, but as described above, sodium thiosulfate and meso ions are more preferred from the viewpoint of substantially eliminating ammonium ions in the processing solution due to environmental problems. Furthermore, by using two or more types of fixing agents in combination, it is possible to perform quicker fixing. For example, it is preferable to use the above-mentioned ammonium thiocyanate, imidazole, thiourea, thioether and the like in addition to ammonium thiosulfate and sodium thiosulfate. In this case, the second fixing agent is 0.1% based on ammonium thiosulfate and sodium thiosulfate. 01-10
It is preferable to add in the range of 0 mol%. The amount of the fixing agent is from 0.1 to 3 per liter of the bleach-fixing solution or the fixing solution.
0 mol, preferably 0.5 to 2.0 mol. Although the pH of the fixing solution depends on the type of the fixing agent, it is generally 3.0 to 3.0.
9.0, especially when a thiosulfate is used.
8 to 8.0 is preferable for obtaining stable fixing performance.

In the processing solution having a fixing ability, sulfites (for example, sodium sulfite, potassium sulfite,
Ammonium sulfite), hydroxylamines, hydrazines, bisulfite adducts of aldehyde compounds (for example, sodium acetaldehyde bisulfite, particularly preferably a compound described in JP-A-3-158848) or JP-A-1
And a sulfinic acid compound described in JP-A-231051. Furthermore, various fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol can be contained. Further, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or organic phosphonic acids to the processing solution having a fixing ability for the purpose of stabilizing the processing solution. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, Cyclohexanediaminetetraacetic acid, 1,
2-propylenediaminetetraacetic acid can be mentioned.
It is also preferable to add a buffer to the bleach-fixing solution or the fixing solution in order to keep the pH of the solution constant. For example, phosphates or imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole, 1-ethyl-imidazole, triethanolamine,
N-allylmorpholine, N-benzoylpiperazine and the like can be mentioned.

It is preferable that the total time of the desilvering step is shorter as long as the desilvering failure does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. The processing solution having the bleaching ability of the present invention is particularly preferably subjected to aeration during processing, since the photographic performance is extremely stably maintained. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Such a diffuser is widely used for an aeration tank in activated sludge treatment. Regarding aeration, Z-121, Using Process C-41, 3rd Edition (1982), BL-1 to BL, issued by Eastman Kodak Company
Items described on page-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened.
The contents described on page 8, upper right column, line 6 to lower left column, line 2 of JP-A-7 can be used as they are.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. Specific examples of the method of strengthening the stirring include a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, and a method described in JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and furthermore, moving the photosensitive material while making the emulsion surface contact the wiper blade provided in the liquid, making the emulsion surface more turbulent, thereby increasing the stirring effect. And a method of increasing the circulation flow rate of the entire processing liquid. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic developing machine used in the present invention is disclosed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-19125.
It is preferable to have the photosensitive material conveying means described in No. 9. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The processing solution having the bleaching ability of the present invention comprises:
The overflow liquid used for the treatment is recovered, and after the components are added to correct the composition, the overflow liquid can be reused. Such a method of use is usually referred to as reproduction, but the present invention can also preferably perform such reproduction. For details of reproduction, see Fujifilm Processing Manual, Fujicolor Negative Film, CN-16 processing (revised in August 1990), page 39, issued by Fuji Photo Film Co., Ltd.
The matters described on page 40 are applicable. The kit for adjusting the processing solution having the bleaching ability of the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied in the form of a powder, and the hygroscopicity is low.
Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be directly added without using excess water.

Regarding the regeneration of the processing solution having the bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver halide photography-" (edited by the Photographic Society of Japan, published by Corona, 1979)
Year) can be used. Specifically, in addition to electric field regeneration, a method for regenerating a bleaching solution with bromic acid, zinc acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using a catalyst, bromite, ozone, etc. No.
In the regeneration by electrolysis, the cathode and the anode are placed in the same bleaching bath, or the anode and the cathode are separated from each other by using a diaphragm to regenerate. And / or regenerating the fixing solution at the same time. The regeneration of the fixing solution and the bleach-fixing solution is carried out by electrolytic reduction of accumulated silver ions. Others
It is also preferable to remove the accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. In order to reduce the amount of washing water used, ion exchange or ultrafiltration is used, and it is particularly preferable to use ultrafiltration.

The various processing solutions used in the present invention are used at 10 ° C. to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. In the case of processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation, an appropriate amount of water or a correction solution or a processing replenisher may be replenished in order to correct the concentration by evaporation. preferable. Although there is no particular limitation on a specific method for performing water replenishment, in particular, JP-A Nos. 1-254959 and 1-25
No. 4960, a separate monitoring tank was installed from the bleaching tank, the amount of water evaporation in the monitoring tank was determined, the amount of water evaporation in the bleaching tank was calculated from the amount of water evaporation, and the amount of evaporation was calculated. A method for replenishing water to a bleaching tank in proportion to 1
No. 248155, No. 3-249644, No. 3-249
No. 645, No. 3-249646, and an evaporation correction method using a liquid level sensor or an overflow sensor are preferable. Water for correcting the evaporation of each processing solution is
Tap water may be used, but it is preferable to use deionized water or sterilized water which is preferably used in the above-mentioned washing step.

Next, a photosensitive material applicable to the present invention will be described. The stabilizing processing solution of the present invention and the processing using the same can be applied to any photosensitive material, but in the present invention, a photosensitive material using various plastic films as a material of a support, for example, a photographic material When applied to a color negative photographic light-sensitive material or a color reversal photographic light-sensitive material, the effect is greatly exhibited. These photosensitive materials are described in JP-A-3-46654 and JP-A-2-85.
No. 4, 2-90151, 4-270344, 5-34889, European Patent Publication 0504609A2
And No. 519190A2. In particular, silver iodobromide containing 0.2 to 20 mol% of silver iodide is preferable as the silver halide used in a color negative photographic light-sensitive material or a color reversal photographic light-sensitive material.

Known photographic additives which can be used in the present invention are described in the following three Research Disclosures, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer 678, right column 3. Spectral sensitizer, page 23-24, page 648, right column, pages 866-868 Color sensitizer 〜Page 649 right column 4. Brightener 24 page 647 page right column 868 5.Fogging prevention 24-25 page 649 page right column 868 870870 page Agents, stabilizers 6.Light absorbers, 25- Page 26 649 Page Right Column 873 Filter ~ Page 650 Left Column Dyes, Ultraviolet Ray Absorbers 7.Stain 25 Page Right Column 650 Page Left Column 872 Inhibitors ~ Right Column 8. Dye Image 25 Page 650 Page Left Column 872 Stabilizer 9. Hardener page 26, page 651, left column, pages 874 to 875 10. Binder page 26, page 651, left column, 873 to 874 11. Plasticizer, page 27, page 650, right column, page 876 Lubricant 12. Coating aid Pp. 26-27, 650, right column, 875-876, surfactant 13.Static, page 27, 650, right column, 876-877, inhibitor 14.Matsuto, 878-879

Suitable supports that can be used in the light-sensitive material of the present invention are described in, for example, RD. No. 17643, page 28, No. 187
No.307105 of No.307105 from the right column of page 647 to the left column of page 648
It is described on page 879. As the material of the support, various plastic films described in JP-A-4-124636, page 5, upper right column, line 1 to page 6, upper right column, line 5 can be used. Preferred are cellulose derivatives (for example, diacetyl). -, Triacetyl-, propionyl-, butanoyl-, acetylpropionyl-acetate) and polyesters described in JP-B-48-40414 (for example, polyethylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene naphthalate). Can be The support of the film used in the present invention can be made of polyethylene terephthalate, a functional material, 199
Polyethylene naphthalate described in the Yearly and February Edition, pages 20 to 28 is preferred. When the light-sensitive material of the present invention is used as a color negative film, the thickness of the support is 70 to 13
0 μm is preferable, and particularly preferably 80 to 120 μm.

In the case where the light-sensitive material of the present invention is used as a color film, the support is described in International Publication WO90 / 04.
No. 205, FIG. Those having the magnetic recording layer described in 1A are preferable. As described in JP-A-4-62543, a support having such a magnetic recording layer preferably has a conductive layer containing zinc, titanium, tin, or the like on one surface. In addition, Japanese Patent Application Laid-Open No.
No. 8 having a stripe magnetic recording layer and having a transparent magnetic recording layer adjacent to the stripe magnetic recording layer can also be used. On top of the magnetic recording layer, JP-A-4-73
No. 737 can also be provided.

In the case where the light-sensitive material of the present invention is used as a color film, the packaging (patrone) for accommodating the color film may be any of those currently used or known, and in particular, US Pat. No. 4,834,306. , F
IG. 1 to FIG. 3 as well as U.S. Pat. No. 4,846,418 and FIG. 1 to FIG. Those described in No. 3 are preferred. The format of the color film used in the present invention is Japanese Industrial Standard "JIS.K-75".
19 (1982), and any known format other than the format described in JP-A-4-287040 can be used.

[0044]

The present invention will be described in detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

Second layer (intermediate layer) Silver iodobromide emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 gelatin 1.04

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.25 silver iodobromide emulsion B silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth layer (medium-speed red-sensitive emulsion layer) Silver iodobromide emulsion Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 gelatin 1.10

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 gelatin 0.90

Ninth layer (high sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

Tenth layer (yellow filter layer) Yellow colloidal silver silver 0.030 Cpd-1 0.16 HBS-1 0.60 gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion C silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10

12th layer (medium speed blue-sensitive emulsion layer) Silver iodobromide emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

13th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion F Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

Fourteenth layer (first protective layer) Silver iodobromide emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, W-1 to W-3, B-4 to B- may be added to each layer to improve the storability, processability, pressure resistance, fungicide / antibacterial property, antistatic property and coatability. 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
Contains iridium and rhodium salts.

[0061]

[Table 1]

In Table 1, (1) Silver iodobromide emulsions A to F were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-19938. (2) Silver bromoiodide emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Sensitization has been applied. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high-pressure electron microscope.

[0063]

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[0069]

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[0070]

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[0074]

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[0075]

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[0076]

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[0077]

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After exposing the color photographic light-sensitive material as described above, it was processed using an automatic developing machine by the method described below (until the cumulative replenishment amount of the stabilizing solution became three times the tank capacity).

(Processing method) Step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C 22 ml 20 liter Bleaching 3 minutes 00 seconds 38 ° C 25 ml 40 liter Water washing (1) 15 seconds 24 ° C From (2) 10 liters to (1) Counterflow piping method Rinse (2) 15 seconds 24 ° C 15ml 10 liters Fixed 3 minutes 00 seconds 38 ° C 15ml 30ml Rinse water (3) 30 seconds 24 ° C From (4) to (3) 10 liter Counter-flow piping system Rinse (4) 30 seconds 24 ° C 1200ml 10 liters Stabilized 30 seconds 38 ° C 20ml 10 liter Dry 4 minutes 20 seconds 55 ° C Replenishment amount is 35mm width per 1m length Rinse (1) to (4 ) Uses water

Next, the composition of the processing solution will be described. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 2.2 Sodium sulfite 4.0 4.8 Potassium carbonate 30.0 39.0 Potassium bromide 1.4 0.3 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 3.1 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 6.0 1.0 liter with water added 1.0 liter pH 10.05 10.15

(Bleaching solution) Tank solution (g) Replenisher (g) Sodium ferric ethylenediaminetetraacetate trihydrate 100.0 120.0 Disodium ethylenediaminetetraacetate 10.0 11.0 3-mercapto-1,2,4-triazole 0.03 0.08 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Add water 1.0 liter 1.0 liter pH (adjusted with ammonia water, HNO ₃ ) 6.0 5.7

(Fixing solution) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Sodium sulfite 20.0 22.0 Sodium thiosulfate aqueous solution (700 g / liter) 295.0 ml 320.0 ml Acetic acid (90%) 3.3 4.0 water 1.0 liter 1.0 liter pH 6.7 6.8

(Stabilizer) Tank liquid / replenisher common (g) Image stabilizer (see Table 2) 0.006 mol ethylenediaminetetraacetic acid 0.03 Surfactant W-8 (50% aqueous solution) 0.7 Gentamicin 0.01 acid (see Table 2) See Table 2. 1.0 liter with water pH 7.0 pH finely adjusted with sodium hydroxide.

Incidentally, stabilizers Nos. 1 to 13 using formaldehyde as an image stabilizer were prepared using formalin. In these stabilizers Nos. 1 to 13, the concentration of free formaldehyde was 0.2%, and in stabilizers Nos. 14 to 26 using A-14 as an image stabilizer, 0.007
%Met. About the photosensitive material processed by the above method,
Dirt on the back surface of the photosensitive material and changes with time of stain were determined by the following method. Soil: The surface of Sample 101 on which the emulsion was not applied at the end of the running was observed to confirm the presence or absence of stain. Evaluation: ：: No generation of dirt. Δ: Slight occurrence of dirt, but no problem in practical use. X: Stain occurred.

Change of stain with time: The density of the photosensitive material processed by the above method was measured, and Dmin measured with blue light (B light) was read from the characteristic curve. Next, the sample after measurement was stored under the following conditions, and Dmin after aging was measured in the same manner. Then, the time-dependent change of the stain of the yellow dye was determined as follows. Storage conditions: 70 ° C, 70%, 4 weeks Stain change over time (ΔD) = (Dmin after storage)-
(Dmin before storage) Further, the stability of the above-mentioned stabilizing solution in an unused state was evaluated by the following method. Stability: The amount of dilution water for the stabilizing solution is 1 liter to 10 ml
Was prepared, filled in a PVC bottle, and aged for 7 weeks at 40 ° C. in a sealed stopper. At this time, the occurrence of sedimentation was confirmed visually. Evaluation: ：: No precipitation occurred. Δ: Some turbidity occurred, but no precipitation occurred. X: Precipitation occurred. Table 2 shows the results obtained by the above method.

[0086]

[Table 2]

From the results shown in Table 2, it can be seen that only in the embodiment of the present invention, no stain is generated, and at the same time, an excellent effect on the stain when storing the processed color image is exhibited. It can also be seen that with respect to the stability of the liquid, the formation of the precipitate can be improved by the embodiment of the present invention. It can be seen that both effects are particularly large and preferable when an image stabilizer having a low free formaldehyde concentration is used. still,
Discoloration of the magenta dye (60 ° C.)
Aged at 20% relative humidity for 2 weeks, magenta concentration 1.5
No fading was observed.

Example 2 The same procedure as in Example 1 was carried out except that the support of the sample 101 of Example 1 of the present application was replaced with the support shown below, and a sample 201 prepared in the same manner as in Example 1 was otherwise used. went. As a result, it was found that, similarly to Example 1, only the aspect of the present invention did not cause stains and exhibited an excellent effect.

(2-1) Preparation of Support Polyethylene terephthalate was uniaxially stretched, and a poly (vinylidene / acrylonitrile / itaconic acid; molar ratio of 92: 5: 3) aqueous dispersion was applied to both surfaces (content after stretching 1.5 g /
m ² ), sodium dodecylbenzenesulfonate (2 mg /
m ² ), silica particles (average particle size 0.3 μm;
m ² ), polystyrene particles (average particle size: 1.0 μm; 2 mg /
m ² ), 2-hydroxy-4,6-dichloro-1,3,5
Triazine (35 mg / m ² ) and trimethylolpropane triaziridine (10 mg / m ² ) were applied and stretched again during drying to undercoat the support to form a first vinylidene chloride layer. At this time, the thickness of the polyethylene terephthalate was 90 μm. After further corona discharge treatment on both surfaces, gelatin (0.2 g / m ² ), poly (degree of polymerization 10) oxyethylene dodecyl ether (2 mg / m ² ),
Compound WA (10 mg / m ² ) was applied to form a support as a second undercoat layer.

(2-2) Preparation of Back Surface The following back layer was applied to one side of the undercoated support prepared in (2-1) (the number corresponding to each component is g / m ² Indicates the amount of coating expressed in units)

A) Back first layer Cobalt-doped iron oxide fine powder (contained as a gelatin dispersion; average particle size 0.08 μm) 0.2 gelatin 3.0 poly (ethyl acrylate) (average diameter 0.08 μm) 1.0 Compound WB 0.1 Compound WC 0.02

B) Back second layer gelatin 0.05 Conductive material SnO ₂ / Sb ₂ O ₃ (9: 1) (particle size 0.15 μm) 0.16 mg sodium dodecylbenzenesulfonate 0.05 0.05

C) Back third layer gelatin 0.5 polymethyl methacrylate (average particle size 1.5 μm) 0.02 cetyl stearate (dispersed in sodium dodecylbenzenesulfonate) 0.01 sodium di (2-ethylhexyl) sulfosuccinate 0.01 A fluorine-containing surfactant was used for the back third layer. The structural formulas of the compounds WA, WB, WC and the fluorine-containing surfactant are shown below.

[0094]

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The coercive force of the back layer of the support obtained here was 960 Oe.

Example 3 After exposing the multilayer color reversal photosensitive material sample 401 described in Example 4 of JP-A-4-359249, the following method was used using an automatic developing machine. (Until three times the tank volume).

(Processing method) Step Processing time Processing temperature Replenishment amount Tank capacity First development 6 minutes 38 ° C 2200ml 12L First water washing 2 minutes 38 ° C 7500ml 4L Inversion 2 minutes 38 ° C 1100ml 4L Color development 6 minutes 38 ℃ 2200ml 12 liters Pre-bleaching 2 minutes 38 ° C 1100ml 4 liters Bleaching 6 minutes 38 ° C 220ml 12 liters Fixed 4 minutes 38 ° C 1100ml 8 liters Second rinsing 4 minutes 38 ° C 7500ml 8 liters Stable 1 minute 38 ° C 1100ml 2 liters drying 2 min 55 ° C. replenishment rate photosensitive material 1 m ² per

Next, the composition of the processing solution will be described. (First developer) Tank solution (g) Replenisher (g) Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 1.5 1.5 Diethylenetriaminepentaacetic acid pentasodium salt 2.0 2.0 Sodium sulfite 30.0 30.0 Hydroquinone mono Potassium sulfonate 20.0 20.0 Potassium carbonate 15.0 20.0 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 2.0 Potassium bromide 2.5 1.4 Potassium thiocyanate 1.2 1.2 Potassium iodide 2.0 mg-Ethylene glycol 13.0 15.0 Add water 1.0 liter 1.0 liter pH 9.60 9.60 pH was adjusted with sulfuric acid or potassium hydroxide.

(Reversal solution) Tank solution (g) Replenisher solution (g) Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3.0 Same as tank solution Stannous chloride dihydrate 1.0 p-amino acid Phenol 0.1 sodium hydroxide 8.0 glacial acetic acid 15 ml Water was added 1.0 liter pH 6.00 pH was adjusted with acetic acid or sodium hydroxide.

(Color developing solution) Tank solution (g) Replenisher (g) Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0 2.0 Sodium sulfite 7.0 7.0 Trisodium phosphate / 12 hydrate 36.0 36.0 Potassium bromide 1.0-Potassium iodide 90 mg-Sodium hydroxide 3.0 3.0 Citrazinic acid 1.5 1.5 N-Ethyl-N- (β-methanesulfamidoethyl) -3-methyl 4-aminoaniline / 3/2 sulfuric acid monohydrate 11.0 11.0 3,6-dithiaoctane-1,8-diol 1.0 1.0 1.0 liter by adding water 1.0 liter pH 11.80 12.00 pH was adjusted with sulfuric acid or potassium hydroxide.

(Pre-bleach solution) Tank solution (g) Replenisher solution (g) Ethylenediaminetetraacetic acid disodium dihydrate 8.0 Same as tank solution Sodium sulfite 6.0 1-thioglycerol 0.4 Add water 1.0 liter pH 6.20 pH Was prepared with acetic acid or sodium hydroxide.

(Bleaching solution) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid, disodium, dihydrate 2.0 4.0 Ethylenediaminetetraacetic acid, Fe, (III), ammonium, dihydrate 120.0 240.0 Potassium bromide 100.0 200.0 Ammonium nitrate 10.0 20.0 Add water 1.0 liter 1.0 liter pH 5.65 5.45 pH was adjusted with nitric acid or sodium hydroxide.

(Fixing solution) Tank solution (g) Replenisher solution (g) Ammonium thiosulfate 80.0 Same sodium sulfite 5.0 sodium bisulfite 5.0 water was added to the tank solution, and 1.0 liter pH 6.60 pH was adjusted with acetic acid or aqueous ammonia.

(Stabilizing solution) Common to tank solution / replenishing solution (g) Image stabilizer (see Table 3) 0.01 mol Ethylenediaminetetraacetic acid 0.03 Surfactant W-7 (50% aqueous solution) 0.7 Gentamicin 0.01 Add water and 1.0 Liters acid (see Table 3) See Table 3 pH 6.0 pH is finely adjusted with sodium hydroxide.

(First Rinse, Second Rinse) The common liquid of the tank liquid and the replenisher was used.

With respect to the photosensitive material processed by the above method,
As in Example 1 of the present application, the change with time of stain and stain was determined. Table 3 shows the results.

[0107]

[Table 3]

From the results shown in Table 3, the acid of the present invention did not adhere to the photosensitive material as compared with the comparative compound in the color reversal film for photography as in Example 1 of the present invention, and the stain during storage of the color image was also reduced. It turns out that it shows an excellent effect. In addition, no difference was observed in the fading of the magenta dye in any of the stabilizers.

[0109]

According to the present invention, it is possible to perform processing using a processing agent which is excellent in liquid stability, prevents adhesion of dirt in continuous processing, and has excellent image storability after processing.

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 11/00 501

Claims (4)

(57) [Claims] (1) having at least one hydroxy group
At least one monobasic organic acid;
Nudsaldehydes, b) hexamethylenetetramine,
(C) N-methylolazoles, (d) azolylmethyl
Luamines, in which (e) the heteroatom is composed of only a nitrogen atom
Azoles, (f) methoxycarbonyl aldehyde
And (g) at least one compound selected from pyridyl aldehydes . (2) having at least one hydroxy group
At least one monobasic organic acid;
Nudsaldehydes, b) hexamethylenetetramine,
(C) N-methylolazoles, (d) azolylmethyl
Luamines, in which (e) the heteroatom is composed of only a nitrogen atom
Azoles, (f) methoxycarbonyl aldehyde
And (g) at least one compound selected from pyridyl aldehydes . 3. The stabilizing solution has a free formaldehyde concentration of 0 to 0.01%.
The stabilizing solution according to the above. 4. The stabilizing solution has a free formaldehyde concentration of 0 to 0.01%.
A method for processing a silver halide color photographic light-sensitive material as described above.