JP2811071B2 - Processing method of silver halide color photographic light-sensitive material for photography - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material for photography (hereinafter sometimes simply referred to as “photosensitive material”). The present invention relates to a bleaching process and a fixing process suitable for the use of a photosensitive material, and is a technique that can be suitably used for a high-sensitivity photosensitive material having a large amount of silver.

[Background of the Invention]

Processing of the photosensitive material basically comprises two steps of color development and desilvering, and desilvering comprises a bleaching and fixing step or a bleach-fixing step. In addition, rinsing processing, stabilization processing, and the like are added as additional processing steps.

In a processing solution having a bleaching ability used in a desilvering step of a photosensitive material, an inorganic oxidizing agent such as a red blood salt or a dichromate is widely used as an oxidizing agent for bleaching image silver.

However, processing solutions having bleaching ability containing these inorganic oxidizing agents have been pointed out with some serious drawbacks. For example, red blood salts and dichromates are relatively excellent in terms of the bleaching power of image silver, but may be decomposed by light to generate harmful cyan ions and hexavalent chromium ions, which cause pollution. It has unfavorable properties for prevention.
Further, the processing liquid containing these inorganic oxidizing agents has a disadvantage that it is difficult to recycle the processing liquid without discarding the waste liquid after the processing.

On the other hand, there are few pollution problems,
In order to meet the demands for simplification and reusability of waste liquids, treatment liquids using an organic acid metal complex such as aminopolycarboxylic acid metal complex as an oxidizing agent have come to be used. However, a processing solution using a metal complex salt of an organic acid has a drawback that the bleaching speed (oxidation speed) of image silver (metal silver) formed in the developing step is slow because of the slow oxidizing power. .

For example, ethylenediaminetetraacetate (II) which is considered to have strong bleaching power among aminopolycarboxylic acid metal complex salts
I) Complex salts are used in some cases as bleaching solutions and bleach-fixing solutions. However, high-sensitivity silver halide color photographic light-sensitive materials mainly composed of silver bromide and silver iodobromide emulsions, especially as silver halides A color paper for photography, a color negative film for photography, and a color reversal film for photography, which contain silver iodide and have a high silver content, have the disadvantage that the bleaching power is insufficient and the bleaching step requires a long time.

Further, in a developing method in which a large amount of photosensitive material is continuously processed by an automatic developing machine or the like, in order to prevent the performance of the bleaching solution from deteriorating due to a change in the component concentration, the components of the processing solution are kept within a certain concentration range. Means are needed.

As such means, in recent years, from the viewpoint of economy and pollution, a so-called concentrated low replenishment method in which these replenishers are concentrated and replenished in a small amount, or another method in which a regenerant is added to an overflow solution and used again as a replenisher has been proposed. Is coming.

In particular, in the bleaching solution, a ferrous organic acid complex formed by bleaching the developed silver, for example, an iron (II) complex of ethylenediaminetetraacetate by ironing an iron (III) complex of ethylenediaminetetraacetate, that is, a ferric organic acid complex A method has been put to practical use in which a regenerating agent for supplementing the deficient component is further added by oxidizing the solution, and then used again as a replenisher.

However, in recent years, so-called compact labs (also known as mini labs) have emerged in order to shorten the processing time of silver halide color photographic materials and reduce collection and delivery costs.
In such a lab, there is a strong need for simplification of the processing and reduction in the installation area of the developing machine, which requires cumbersome labor and management, and regenerating processing that requires a processing space is not preferable.

Therefore, a rich low replenishment method in which low replenishment is performed without performing regeneration processing is preferable, but when the replenishment amount of the bleaching solution is extremely reduced, the concentration of the color developing solution component brought into the bleaching solution increases, and concentration by evaporation is performed. And the accumulation of color developing solution components is further increased. As described above, when the concentration of the color developing solution component in the bleaching solution increases, the mixing ratio of the color developing agent or the sulfite, which is a reducing component, increases, and the bleaching reaction is suppressed. Become. In order to improve these shortcomings, Research Disclosure No.24023,
A technique using a specific ferric aminopolycarboxylic acid complex salt and a mixture thereof described in JP-A-62-222252 has been proposed.

However, it has been found that these techniques have various disadvantages. For example, a ferric complex of 1,3-diaminopropanetetraacetic acid described in the above-mentioned literature or patent publication, when bleaching a high-sensitivity light-sensitive material having a large amount of silver for a long period of time, causes bleaching fog. Will happen. That is, the use of these as a bleaching agent can achieve the desired purpose if bleaching or bleach-fixing of a low-sensitivity photosensitive material mainly composed of a silver chlorobromide emulsion. Highly sensitive color sensitized materials mainly composed of silver iodide or silver iodobromide emulsions and color sensitized, in particular, color negative photographic materials for ultra-high sensitivity photography using high silver content emulsions (for example, ASA sensitivity 400 to 3200) In the case of processing, there is a problem that bleaching fog occurs. In particular, this disadvantage becomes even greater when the replenishment amount of the bleaching solution is reduced. Further, it has been found that this tendency is increasingly emphasized when the concentration of the color developing agent used in the color developing process which is a pre-process of the bleaching process is 1.5 × 10 ^-2 mol or more.

The present inventors have found that the bleaching fog increases with the bleaching processing time, so that a bleaching processing time of 90 seconds or less is desirable. Did not sufficiently occur, and it was found that there was a problem that poor recoloring occurred.

Another problem when using a ferric complex of 1,3-diaminopropanetetraacetic acid as a bleaching agent is that when the bleaching solution is brought into a processing solution having a fixing ability in the next processing step, the processing There is a problem that the storage stability of the liquid is deteriorated to a large extent.

Therefore, there is a need for a technology capable of processing a photosensitive material having a high sensitivity and a high silver amount without causing bleaching fog and poor recoloring and without deteriorating the storage stability of the fixing solution when the bleaching solution is mixed into the fixing solution. ing.

[Object of the invention]

An object of the present invention is to provide a method for processing a light-sensitive material in which a bleaching solution is processed immediately after color development and then processed with a fixing solution, whereby the bleaching process is accelerated, and has bleaching fog, poor recoloring and fixing ability. An object of the present invention is to provide a processing method for a photosensitive material in which deterioration due to mixing of a processing solution into a bleaching solution is improved.

[Configuration of the invention]

The processing method of the present invention for achieving the above object is a processing method of a photographic light-sensitive material, in which a bleaching solution is processed immediately after color development and then processed with a fixing solution, wherein the bleaching solution is represented by the following general formula (A). Contains a ferric complex salt of the compound shown, and has a bleaching solution treatment time of 90 seconds or less,
The fixing solution has a buffering agent having a buffering ability at pH 6.0 to 8.5.
It is characterized by containing 0.5 mol / content and having a pH of 6.0 to 8.5.

In the general formula [A], A ₁ , A ₂ , A ₃ and A ₄ may be the same or different, and each represents -CH ₂ OH, -COOM or -P
Represents O ₃ M ₁ M ₂ . M, M ₁ and M ₂ are each a hydrogen atom, a sodium atom, a potassium atom or an ammonium group. X
Represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.

[Specific configuration of the invention]

First, the compound represented by the general formula [A] will be described in detail.

In the general formula [A], a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms represented by X is, for example, a propylene group,
Examples thereof include a butylene group, a trimethylene group, a tetramethylene group, a pentamethylene group and the like, and a group in which a hydroxyl group is substituted as a substituent.

Preferred specific examples of the compound represented by the formula [A] are shown below.

And sodium salts of these (A-1) to (A-8),
Potassium salt or ammonium salt.

From the viewpoint of the effects of the present invention, ammonium salts of these ferric complex salts are preferably used.

Among the compound examples, those particularly preferably used in the present invention include (A-1), (A-2) and (A-
4) and (A-7), and particularly preferred is (A-1).

The ferric complex salt of the compound represented by the general formula [A] is used in an amount of 0.01 mol or more per bleaching solution, more preferably
It is in the range from 0.01 mol to 0.3 mol, particularly preferably from 0.05 mol to 0.25 mol.

In the bleaching solution of the present invention, preferred bleaching agents used in combination with the compound represented by the above general formula [A] include the following.

(A′-1) Ethylenediaminetetraacetic acid or a salt thereof (a salt of ammonium, sodium, potassium, triethanolamine, etc.) (A′-2) trans-1,2-cyclohexanediaminetetraacetic acid or a salt thereof (〃) (A '-3) Dihydroxyethylglycinic acid or its salt (そ の) (A'-4) Ethylenediaminetetrakismethylenephosphonic acid or its salt (〃) (A'-5) Nitrilotrismethylenephosphonic acid or its salt (〃) (A '-6) Diethylenetriaminepentakismethylenephosphonic acid or its salt (〃) (A'-7) Diethylenetriaminepentaacetic acid or its salt (〃) (A'-8) Ethylenediaminediorthohydroxyphenylacetic acid or its salt (〃) ( A'-9) Hydroxyethylethylenediamine triacetic acid or a salt thereof (〃) (A'-10) Diaminedipropionic acid or its salt (ジ) (A'-11) ethylenediaminediacetic acid or its salt (〃) (A'-12) glycol ether diaminetetraacetic acid or its salt (〃) (A'-13) hydroxy Ethyl iminodiacetic acid or its salt (〃) (A'-14) Nitrilotriacetic acid or its salt (〃) (A'-15) Nitrilotripropionic acid or its salt (〃) (A'-16) Triethylenetetramine hexa Acetic acid or a salt thereof (〃) (A′-17) Ethylenediamineditetrapropionic acid or a salt thereof (〃) The above-mentioned compounds can be exemplified, but of course, the compounds are not limited to these exemplified compounds.

In these compounds, A'-1, A'-2, A'-
7 and A'-12 are preferred.

These aminopolycarboxylic acid iron (III) complex salts may be used in the form of a complex salt, or may be used in the form of an iron (III) salt such as sulfuric acid secondary salt.
An iron (III) ion complex salt may be formed in a solution using iron, ferric chloride, ferric acetate, ferric ammonium sulfate, ferric phosphate and the like and an aminopolycarboxylic acid or a salt thereof in a solution. When used in the form of a complex salt, one kind of complex salt may be used, or two or more kinds of complex salts may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and an aminopolycarboxylic acid, one or more ferric salts may be used. Further, one or more aminopolycarboxylic acids may be used. In any case, the aminopolycarboxylic acid may be used in an excess amount to form an iron (III) ion complex salt. Aminopolycarboxylic acid and iron complex salt may be used as ammonium salt, sodium salt, potassium salt, or triethanolamine salt,
These may be used in combination of two or more.

The bleaching solution containing the iron (III) ion complex may contain a metal ion complex salt of cobalt, copper, nickel, zinc, etc. other than iron.

The bleaching solution of the present invention may contain a buffer. As the buffer preferably used, an organic compound represented by the following general formula (I), (II) or (III),
Inorganic compounds such as compounds containing at least one nitrogen, phosphorus or boron atom.

General formula [I] A-COOH In the formula, A represents a hydrogen atom or an organic compound group.

In formula (III) B-PO ₃ H ₂ Formula, B represents a hydrogen control atom or an organic compound group.

In the formula, C ′, D and E each represent a hydrogen atom or an organic compound group. However, at least one of C, D and E is an organic compound group.

Next, specific examples of the buffering agent preferably used in the present invention will be described.

Preferred compounds as fatty acids are acrylic acid, adipic acid, acetylenedicarboxylic acid, acetoacetic acid, azelaic acid, isocrotonic acid, isopropylmalonic acid, isobutyric acid, itaconic acid, isovaleric acid, ethylmalonic acid, caproic acid, formic acid, valeric acid , Citric acid, glycolic acid, glutaric acid, crotonic acid, chlorofumaric acid, α-chloropropionic acid, gluconic acid, glyceric acid, β-chloropropionic acid, succinic acid, cyanoacetic acid, diethylacetic acid, diethylmalonic acid, dichloroacetic acid, Citraconic acid, dimethylmalonic acid, oxalic acid, d-tartaric acid, meso-tartaric acid, trichlorolactic acid, tricarballylic acid, trimethylacetic acid, lactic acid,
Vinyl acetic acid, pimelic acid, pyrotartaric acid, grape acid, fumaric acid, propionic acid, propylmalonic acid, maleic acid,
Malonic acid, mesaconic acid, methylmalonic acid, monochloroacetic acid, n-butyric acid, malic acid, aspartic acid, DL-alanine, glutamic acid, 3,3-dimethyl-glutaric acid and the like.

Preferred compounds having an acid having a cyclic structure include ascorbic acid, atropeic acid, allocinnamic acid, benzoic acid, isophthalic acid, oxybenzoic acid (m-, p-), and chlorobenzoic acid (o-, m-, p-). ), Chlorophenylacetic acid (o-, m
-, P-), cinnamic acid, salicylic acid, dioxybenzoic acid (2,3,2,4,2,5,2,6,3,4,3,5), cyclobutane-1,
1-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid (trans-, cis-), cyclolopropane-1,1-dicarboxylic acid, cyclopropane-1,2-dicarboxylic acid (trans
-, Cis-), cyclohexane-1,1-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid (trans-, cis-
-), Cyclohexylacetic acid, cyclopentane-1,1-dicarboxylic acid, 3,5-dinitrobenzoic acid, 2,4-dinitrophenoldiphenylic acid, sulfanilic acid, terephthalic acid, toluic acid (o-, m-, p- ), Naphthoic acid (α
-, Β-) nicotinic acid, nitroanisole (o-, m
-, P-), nitrobenzoic acid, nitrophenylacetic acid (o
-, M-, p-), p-nitrophenetol, pyromucoic acid, uric acid, hippuric acid, barbituric acid, picolinic acid, bourolic acid, phenylacetic acid, phenylic acid, phthalic acid, fluorbenzoic acid (o-, m- -, P-), bromobenzoic acid (o
-, M-, p-), hexahydrobenzoic acid, benzylic acid, dl-madelic acid, meditylene acid, methoxybenzoic acid (o-, m-, p-), methoxycinnamic acid (o-, m
-, P-), p-methoxyphenylacetic acid, gallic acid, aminobenzoic acid (o-, m-, p-) and the like.

Preferred compounds as amine compounds are isoamylamine, isobutylamine, isopropylamine, ethylamine, ethylenediamine, diisoamylamine, diisobutylamine, diethylamine, diethylenetriamine, dipropylamine, dimethylamine, tetraethylenepentamine, tetramethylenediamine, triethylamine, Trimethylamine, trimethyldiamine, m
-Butylamine, sec-butylamine, tert-butylamine, m-propylamine, pentamethylenediamine,
Hexamethylenetetramine, quinoline, o-toluidine, aminobenzenesulfonic acid (o-, m-, p-),
N-methylbenzylamine, methylbenzylamine (o
-, M-, p-), 2-methylpiperidine, N-methoxybenzylamine, methoxybenzylamine (o-, m-
-, P-), benzylamine, coniine, diethylbenzylamine, cyclohexylamine, piperazine and the like.

Preferred inorganic acids include nitrous acid, phosphorous acid, hypophosphorous acid, boric acid, phosphoric acid, pyrophosphoric acid, triphosphoric acid, metatriphosphoric acid, polyphosphoric acid, polymetaphosphoric acid, and the like.

Preferred compounds among other organic compounds are N- (2-
Acetamido) iminodiacetic acid, N- (2-acetamido) -aminoethanesulfonic acid, bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane,
-(N-morpholino) ethanesulfonic acid, 3- (N-morpholino) -2-hydroxypropanesulfonic acid, piperazine-N, N'-bis (2-ethanesulfonic acid), ethylenediaminediacetic acid, ethylenediamine-2-propion Acid, β-aminoethyliminodiacetic acid and the like, and other preferable organic phosphoric acids include aminomethylphosphonic acid-N, N-diacetic acid, 2-phosphonoethyliminodiacetic acid, and 2-phosphonobutane-1,2. , 4-tricarboxylic acid, and the like.

Among the above compounds, more preferred are fatty acids, acids having a cyclic structure, amine compounds, and inorganic salts, and particularly preferred are fatty acids and amine compounds.

In addition, among organic acids, acetic acid is slightly inferior in effect to the above compounds.

However, at least 40% (mole ratio), preferably at least 50% (mole ratio) of the ferric aminopolycarboxylate (or phosphonic acid) acetate contained as a bleaching agent is at least 50% (molar ratio) of the compound represented by the general formula [A]. When the compound is a diiron complex salt, or when the ferric complex salt of the compound represented by the general formula [A] is 0.2 mol / or more, the acetic acid content is large in the range of 0.5 to 3 mol /, preferably 0.8 mol / l. It has been found that in the range of ２2 mol / mol, it is extremely effective for the liquid stability (the effect of preventing suspended matter).

The pH of the bleaching solution of the present invention is in the range of 3 to 7, and from the viewpoint of the effect of the present invention, the pH is particularly preferably in the range of 4 to 6. Most preferred is the pH range 4.5-5.8.

The processing temperature of the bleaching solution of the present invention is preferably 5 ° C to 80 ° C,
In particular, it is preferably used at 20 ° C to 45 ° C, more preferably 25 ° C to 42 ° C.

The preferred replenishment amount of the bleaching solution according to the present invention is 1 m ² of the light-sensitive material.
20 ml to 500 ml, particularly preferably 30 ml to 350 ml, more particularly preferably 40 ml to 300 ml, most preferably 50 ml to 250 ml.

It is preferable that a halide such as ammonium bromide or ammonium chloride is usually added to the bleaching solution of the present invention.

The bleaching solution of the present invention may contain various fluorescent whitening agents, antifoaming agents or surfactants.

If the processing time with the bleaching solution in the present invention exceeds 90 seconds, the tendency to cause bleaching fog increases.

This processing time is preferably 80 seconds or less, more preferably 70 seconds or less. On the other hand, the lower limit of this processing time is
The time required for sufficient bleaching may be sufficient, and varies depending on conditions such as the type of photosensitive material and processing temperature.

A so-called fixing agent is essential for the fixing solution according to the present invention.

As a fixing agent, a compound which reacts with silver halide to form a complex salt of an aqueous solution, for example, thiosulfate such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate; or halogenated compounds such as thiourea, thioether, or iodide.

The fixing solution according to the present invention contains a buffer having a buffering ability at pH 6.0 to 8.5 (hereinafter, referred to as “buffer of the present invention”). The term `` buffer having a buffering ability at pH 6.0 to 8.5 '' in the definition of the buffer of the present invention refers to the pH of a fixer having a pH of 6.0 to 8.5.
Refers to a buffer having an effect of increasing the buffering capacity for

The buffer of the present invention can be selected from compounds having a pKa value (at 25 ° C. and an ionic strength of 0) in the range of 5.0 to 9.5. Specific examples of the compounds are shown below.

Malic acid, pyridine, p-toluidine, phthalic acid, piperazine, succinic acid, malonic acid, uric acid, tetraethylethylenediamine, 2- (N-morpholino) ethanesulfonic acid, maleic acid, 3,3-dimethylglutaric acid, carbonic acid, 4-hydroxymethylimidazole, citric acid, orthophosphorous acid, N- (2-acetamido) iminodiacetic acid, pyrophosphoric acid, N, N'-bis (3-sulfopropyl) ethylenediamine, N- (2-acetamido) -2 -Aminoethanesulfonic acid, glycerol-2-phosphonic acid, ethylenediamine, imidazole, phosphoric acid, 4-methylimidazole, N-2-hydroxyethylpiperazine-N '
-2-ethanesulfonic acid, N-ethylmorpholine, triethanolamine, mono-tris-2-hydroxyethylimino-tris (hydroxymethyl) methane, 5,5-
Diethyl barbituric acid, tris (tris (hydroxymethyl) aminomethane, 1,4-bis (3-sulfopropyl) piperazine, glycylglycine, 2,5-dimethylimidazole, tris (hydroxyethyl) methylaminopropanesulfonic acid, Tetrakis- (2-hydroxyethyl) ethylenediamine, N-methyldiethanolamine, 2-amino-2-methyl-1,3-propanediol, diethanolamine, 4-phenolsulfonic acid,
2-aminoethylsulfonic acid, alanine, boric acid, tetraethylenediamine, ethanolamine, and salts thereof. These compounds may be used in combination of two or more.

Among these, particularly preferred buffers are carbonic acid, phosphoric acid,
Boric acid, citric acid, imidazole, triethanolamine and ethylenediamine and salts thereof.

The addition amount of the buffer of the present invention is
0.01 mol / -0.5 mol /, 0.05-0.3 mol /
Is particularly preferred.

The fixing solution according to the present invention may contain a buffer other than the buffer according to the present invention.

The fixing solution according to the present invention preferably further contains a large amount of a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like. It is also possible to appropriately add a pH buffer such as a borate, an oxalate, an acetate, a carbonate, a phosphorus acetate, or the like which is known to be added to a normal fixing solution such as an alkylamine or a polyethylene oxide. it can.

The fixing agent is used in an amount of 0.1 mol or more per processing solution, and is preferably 0.6 mol or more from the viewpoint of the effects of the present invention.
It is used in a range of 4 mol, particularly preferably in a range of 1.9 mol to 3.0 mol, particularly preferably in a range of 1.1 mol to 2.0 mol.

In the present invention, air or oxygen may optionally be blown in the processing bath and in the processing replenisher storage tank to increase the activity of the bleaching solution or the fixing solution, or a suitable oxidizing agent, for example, Hydrogen peroxide, bromate, sulfate, etc. may be added as appropriate.

In carrying out the method of the present invention, silver may be recovered from the fixing solution by a known method. For example, electrolysis (French patent 2,
299,667), a precipitation method (described in JP-A-52-73037, a German patent 2,331,220), and an ion-exchange method (described in JP-A-51-1).
No. 7114, German Patent 2,548,237) and metal replacement method (UK Patent 1,353,805) can be effectively used.

It is particularly preferable to recover silver in-line from the tank liquid, because the rapid processing property is further improved. However, silver may be recovered from the overflow waste liquid and reused.

A remarkable effect can be obtained when the replenishing amount of the fixing solution according to the present invention is ^{20 to} 650 ml, particularly 30 to 400 ml per 1 m ^{2 of the} photographic material.

During the fixing according to the present invention, iodide (ammonium iodide, potassium iodide, sodium iodide, lithium iodide, etc.) and / or thiocyanate (eg, sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, etc.) ) When 0.1 to 10 g / 9 is contained, the effect of the present invention is further promoted. Especially 0.3-5 g /, especially 0.5
Good results are obtained at 33 g /, most preferably 0.8-2 g /.

The fixing solution of the present invention may contain a sulfite and a sulfite-releasing compound. Examples of the sulfite-releasing compound include potassium sulfite, sodium sulfite, and ammonium sulfite.
Examples thereof include ammonium bisulfite, potassium bisulfite, sodium bisulfite, potassium metabisulfite, sodium metabisulfite, and ammonium metabisulfite. Furthermore, compounds represented by the following general formula [B-1] or [B-2] are also included.

In the formula, R ₁₇ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₁₈ is an optionally substituted alkyl group having 1 to 5 carbon atoms, M is an alkali metal atom, and R ₁₉ and R ₂₀ are each a hydrogen atom Or, an alkyl group having 1 to 5 carbon atoms which may be substituted, and n represents an integer of 0 to 4.

Preferred specific examples of the compounds represented by formulas [B-1] and [B-2] are shown below.

B-1 Sodium formaldehyde sodium bisulfite B-2 Acetaldehyde sodium bisulfite B-3 Propionaldehyde sodium bisulfite B-4 Butyraldehyde sodium bisulfite B-5 Succinic aldehyde sodium bisulfite B-6 Glutaraldehyde bis sodium bisulfite B- 7 β-Methylglutaraldehyde bisulfite sodium bisulfite B-8 Maleic dialdehyde bisulfite sodium sulfite
The amount of sulfurous acid is preferably at least 0.1 mole per mole, preferably in the range of 0.12 mole / -0.65 mole /
A range of 15 mol / to 0.50 mol / is particularly preferred. Particularly preferred is a range of 0.20 mol / to 0.40 mol /. However, the number of moles of these sulfites and the sulfite-releasing compound is shown in terms of sulfurous acid.

The processing time of the fixing solution is preferably 3 minutes and 10 seconds or less, particularly preferably 10 seconds to 2 seconds, in view of the effects of the present invention.
Minutes in the range of 40 seconds, particularly preferably 20 seconds to 2 minutes
The range is 10 seconds.

In the processing method of the present invention, it is preferable to apply forced stirring to the bleaching solution and the fixing solution. The reason for this is not only that the effects of the object of the present invention can be achieved more favorably, but also from the viewpoint of rapid processing suitability.

Such forced liquid stirring is described in the specification of the patent application filed by the applicant of the present invention (hereinafter referred to as the earlier patent application filed by the present applicant) on Feb. 29, 1988, pp. 64 to 68.

Preferred specific processing method steps of the processing method according to the present invention are shown below. However, the present invention is not limited thereto. (1) Color development → bleaching → fixing → washing (2) Color developing → bleaching → fixing → washing → stable (3) Color developing → bleaching → fixing → stable (4) Color developing → Bleaching → Fixing → First stable → Second stable Among these steps, (3) and (4) are particularly preferable, and (3) and (4) are particularly preferable.

The color developer according to the present invention may contain an alkali agent usually used in the developer, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. And further contains various additives such as benzyl alcohol, alkali metal silver halides such as potassium bromide or potassium chloride, or development regulators such as citrazic acid, and preservatives such as hydroxyamine or sulfite. You may.

Furthermore, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide and dimethylsulfoxide can be appropriately contained.

The pH of the developer according to the present invention is usually 7 or more, and more preferably about 9 to 13.

In the color developer used in the present invention, if necessary, hydroxylamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, bentose or Hexose, pyrogallol-1,3
-Dimethyl ether or the like may be contained.

In the color developing solution according to the present invention, various chelating agents can be used in combination as a sequestering agent.
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid as the chelating agent,
Organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid; aminopolyphosphonic acids such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid; oxycarboxylic acids such as citric acid or gluconic acid; 2-phosphonobutane-1 And phosphonic acids such as 2,4-tricarboxylic acid and polyphosphoric acids such as tripolyphosphoric acid and hexametaphosphoric acid.

The color developing solution of the present invention has a color developing agent concentration of 1.5
It is preferably at least × 10 ^-2 mol /, more preferably at least 2.0 × 10 ^-2 mol /.

In the present invention, the effect of the object of the present invention is particularly improved when the treatment is carried out with a stabilizer followed by a stabilizer.

When the method of the present invention includes a treatment with a stabilizing solution, the replenishing amount of the stabilizing solution is 1 to 80 times the carry-in amount from the previous bath per unit area of the photographic color photographic light-sensitive material to be processed, and particularly 2 to
Although it is preferably 60 times, the concentration of the pre-bath component (fixing solution) in the stabilizer is more preferably 1/500 or less, particularly preferably 1/1000 or less, in the last tank of the stabilizer. Further, the treatment tank of the stabilization tank is configured to have a ratio of 1/500 to 1 / 100,000, and more preferably 1/2000 to 1 / 50,000, from the viewpoints of low pollution and storage stability of the liquid.

The stabilization tank is preferably composed of a plurality of tanks, and it is preferable that the plurality of tanks have two to six layers.

In the case where the number of the stabilization treatment layers is two or more and six or less, the counter current method (a method of supplying the solution to the post-bath and overflowing from the pre-bath) is advantageous in the present invention, especially from the viewpoint of low pollution. preferable. Particularly preferably 2 to
Three tanks, more preferably two tanks.

The amount of processing solution brought in from the pre-bath varies depending on the type of photosensitive material, the transport speed of the automatic processor, the transport method, the squeeze method on the surface of the photosensitive material, and the like. for, amount carried is 50 to 150 / m ^2, replenishment rate effect is more pronounced in the present invention for this amount carried is in the range of 50ml / ² ~4.0 / m ^2, the effect is particularly remarkable supplement the amount is 200~1500ml / m ²
In the range.

The processing temperature of the processing by the stabilizer is 15 to 60 ° C, preferably
The range of 20 to 45 ° C is good.

Various kinds of chelating agents may be contained in the stabilizer. The details of the chelating agent are described in the specification of the earlier application filed by the present applicant on pages 73 to 82.

The pH value of the stabilizer is preferably in the range of pH 4.0 to 9.0, more preferably in the range of pH 4.5 to 9.0, particularly preferably in the range of pH 4.5 to 9.0, for the purpose of improving image storability, in addition to the effects of the present invention.
The pH is in the range of 5.0 to 8.5.

As the pH adjuster that can be contained in the stabilizing solution, any commonly known alkali agent or acid agent can be used.

Stabilizers include organic acid salts (citric acid, acetic acid, succinic acid,
Oxalic acid, benzoic acid, etc.), pH adjusters (phosphate, borate, hydrochloric acid, sulfate, etc.), surfactants, preservatives, Bi, Mg,
Metal salts such as Zn, Ni, Al, Sn, Ti, and Zr can be added. The amount of these compounds added depends on the stability of the bath according to the invention.
Any combination of amounts necessary to maintain the pH and not adversely affect the storage stability and precipitation of the color photographic image may be used.

Antibacterial agents preferably used in the stabilizing solution include hydroxybenzoic acid ester compounds, phenolic compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, and ammonium compounds. Urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, amino acid compounds, active halogen releasing compounds and benzotriazole compounds.

The details of these anti-binders are described in the specification of the earlier application filed by the present applicant on pages 84-90.

It is preferable to use water which has been deionized in advance for the water used for the stabilizing solution, since the anti-blur property of the stabilizing solution, the stability of the stabilizing solution, and the image storability are improved. As a means of the deionization treatment, any means may be used as long as the dielectric constant of the washed water after the treatment is 50 μs / cm or less, or Ca and Mg ions are 5 ppm or less, for example, an ion exchange resin or a reverse osmosis membrane. It is preferable to use the treatment alone or in combination. The ion exchange resin and the reverse osmosis membrane are described in detail in JP-A-87-1984, but it is preferable to use a strongly acidic H-type cation exchange resin and a strongly basic OH-type anion exchange resin.

In the present invention, when the salt concentration in the stabilizing solution is 1,000 ppm or less, preferably 800 ppm or less, the washing effect is enhanced, and the white background is improved and the anti-blur property is excellent.

The processing time of the stabilizing solution in the present invention is 2 minutes or less, preferably 1 minute and 30 seconds or less, particularly preferably 1 minute or less, for achieving the effects of the present invention.

The halogen composition in the light-sensitive material to which the method for processing a light-sensitive material of the present invention is not limited, but the average silver iodide content of all silver halide emulsions is preferably 0.1 to 15 mol%. Preferably it is 0.5 to 12 mol%, particularly preferably 3 to 10 mol%.

In the processing method of the light-sensitive material of the present invention, the average particle size of the silver halide emulsion in the light-sensitive material is not limited,
μm or less, more preferably 0.1 μm to 1.0 μm
m, particularly preferably 0.2 μm to 0.6 μm.

In the method for processing a light-sensitive material of the present invention, the lower limit of the total dry film thickness of all the hydrophilic colloid layers of the light-sensitive material (hereinafter referred to as the film thickness of the emulsion surface) is determined by the amount of the silver halide emulsion, coupler, oil agent, There is a limit depending on the agent and the like, and the preferred thickness of the emulsion surface is 10 to 50 μm, more preferably 15 to 60 μm.
m.

The thickness is preferably 14 μm or more from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support. The color sensitivity differs from that of the emulsion layer, and 20 μm from the emulsion layer to the lower end of the emulsion layer close to the support.
μm or more is preferred.

The photosensitive material according to the present invention is an internal development system in which a coupler is contained in the photosensitive material (US Pat. No. 2,376,679,
No. 2,801,171), and any coupler generally known in the art can be used. For example, cyan couplers include those having a naphthol or phenol structure as a base and forming an indoaniline dye by coupling, and magenta couplers having a 5-pyrazolone ring having an active methylene group as a skeleton structure and pyrazoloazole-based compounds. Examples of the yellow coupler include benzoylacetoanilide, pivalylacetoanilide, and acylacetoanilide structures having an active methylene ring, and those having a substituent at the coupling position and those having no substituent can be used. . As described above, as the coupler, any of a so-called 2-equivalent coupler and a 4-equivalent coupler can be applied.

Hereinafter, couplers that are preferably used to more effectively achieve the effects of the present invention will be described in detail.

As the cyan coupler, the following general formulas [CA], [C
-B] and [CC].

In the formula, R ₁ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and Y is In a group represented by (wherein R ₂ is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R ₃ and .R ₂ represents a group represented by a hydrogen atom or R ₂
R ₃ may be the same or different,
A 6-membered heterocyclic ring may be formed. ) And Z represent a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent.

R ₁ is -CONR ₄ R ₅ , -NHCOR ₄ , -NHCOOR ₆ , -NHSO ₂ R ₆ ,
-NHCONR ₄ R ₅ or -NHSO ₂ NR ₄ R ₅ , R ₂ is a monovalent group, R ₃ is a substituent, X is a hydrogen atom or a group which is released by reaction with an oxidized aromatic primary amine developing agent, l is 0 or 1, m is 0
An integer of 3, R ₄ and R ₅ represent a hydrogen atom, an aromatic group, an aliphatic group or a heterocyclic group, R ₆ represents an aromatic group, an aliphatic group or a heterocyclic group, and when m is 2 or 3, Each R ₃ may be the same or different, may combine with each other to form a ring, or R ₄
And R ₅ , R ₂ and R ₃ , and R ₂ and X may combine to form a ring.
However, when 1 is 0, m is 0, R ₁ is -CONHR ₇ , and R _{7 is}
Represents an aromatic group.

First, the general formulas [CA] and [CB] will be described. In the formula, Y is Is a group represented by Here, R ₁ and R ₂ are each an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (eg, each group of methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group, preferably an alkyl group having 2 to 20 carbon atoms. An alkenyl group (such as an allyl group or peptadecenyl group), a cycloalkyl group, preferably a 5- to 7-membered ring (eg, cyclohexyl);
An aryl group (for example, phenyl group, tolyl group, naphthyl group, etc.), a heterocyclic group, preferably a 5- to 6-membered ring group containing 1 to 4 nitrogen, oxygen or sulfur atoms (for example, furyl, thienyl, Benzothiazolyl group).

R ₃ represents a hydrogen atom or a group represented by R ₂ . R ₂ and R ₃
And may combine with each other to form a 5- to 6-membered heterocyclic ring. Incidentally, any substituent can be introduced into R ₁ and R ₂ , for example, an alkyl group having 1 to 10 carbon atoms (for example, methyl,
i-propyl, i-butyl, t-butyl, t-octyl, etc.), an aryl group (eg, phenyl, naphthyl, etc.), a halogen atom (fluorine, chlorine, bromine, etc.), a cyano, nitro, sulfonamide group (eg, methanesulfone) Amide,
Butanesulfonamide, p-toluenesulfonamide, etc.), sulfamoyl group (methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl group (eg, methanesulfonyl, p-toluenesulfonyl, etc.), fluorosulfonyl group, carbamoyl group (eg, dimethyl Carbamoyl, phenylcarbamoyl, etc.), oxycarbonyl group (eg, ethoxycarbonyl, phenoxycarbonyl, etc.), acyl group (eg, acetyl, benzoyl, etc.), heterocyclic group (eg, pyridyl group, pyrazonyl group, etc.), alkoxy group, aryloxy group, An acyloxy group and the like can be mentioned.

In the general formulas [CA] and [CB], R ₁
Represents a ballast group necessary for imparting diffusion resistance to a cyan coupler represented by the general formulas [CA] and [CB] and a cyan dye formed from the cyan coupler. It is preferably an alkyl group having 4 to 30 carbon atoms, an aryl group, an alkenyl group, a cycloalkyl group or a heterocyclic group. For example, a linear or branched alkyl group (for example, t-butyl, n-octyl, t-octyl, n-dotesyl, etc.), a 5-membered or 6-membered heterocyclic group and the like can be mentioned.

In the general formulas [CA] and [CB], Z
Represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of an N-hydroxyalkyl-substituted-p-phenylenediamine derivative color developing agent. For example, a halogen atom (eg, chlorine, bromine, fluorine, etc.), a substituted or unsubstituted alkoxy group, an aryloxy group, a heterocyclic oxy group,
An acyloxy group, a carbamoyloxy group, a sulfonyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfonamide group and the like are mentioned.More specific examples are U.S. Pat.No. 3,741,563 and JP-A-47-37425. ,
JP-B-48-36894, JP-A-50-10135, 50-117422
No. 50-130441, No. 51-108841, No. 50-120343
No. 52-18315, No. 53-105226, No. 54-14736,
No. 54-48237, No. 55-32071, No. 55-65957, No. 56
No.-1938, No.56-12643, No.56-27147, No.59-1460
No. 50, No. 59-166956, No. 60-24547, No. 60-35731
And No. 60-37557.

In the present invention, a cyan coupler represented by the general formula [CD] is preferable.

In the general formula [CD], R ₄ is a substituted or unsubstituted aryl group (particularly preferably a phenyl group). When the aryl group has a substituent, the substituent includes -SO
₂ R ₅ , halogen atom (fluorine, chlorine bromine, etc.), -CF ₃ ,-
_{NO 2, -CH, -COR 5,} -COOR 5, -SO 2 OR 5 And at least one substituent selected from the group consisting of:

Here, R ₅ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, each group of methyl, ethyl, t-butyl, dodecyl and the like), an alkenyl group, preferably 2 to 20 carbon atoms.
Alkenyl group (allyl group, peptadecenyl group, etc.), cycloalkyl group, preferably one having a 5- to 7-membered ring (eg, cyclohexyl), aryl group (eg, phenyl group,
R ₆ is a hydrogen atom or a group represented by R ₅ .

Compounds suitable as the cyan coupler of the present invention represented by the general formula [CD] are those in which R ₄ is a substituted or unsubstituted phenyl group, and the substituent on the phenyl group is cyano, nitro, or —SO ₂ R ₇ (R ₇ is an alkyl group) A compound such as a halogen atom or trifluoromethyl.

In the general formula [CD], Z and R ₁ each represent the general formula [C
-A] and [CB]. Preferred examples of the ballast group represented by R ₁ are those represented by the following general formula [C-
E].

In the formula, J represents an oxygen atom, a sulfur atom or a sulfonyl group, k represents an integer of 0 to 4, 1 represents 0 or 1, and k represents
Is 2 or more, two or more R _{9 's} may be the same or different, and R ₈ represents a straight or branched chain having 1 to 20 carbon atoms and a substituted alkylene group such as an aryl group; ₉ represents a monovalent group, preferably a hydrogen atom, a halogen atom (for example, chlorine or bromine), an alkyl group, preferably a linear or branched alkyl group having 1 to 20 carbon atoms (for example, methyl, t-butyl, t- -Pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.), aryl group (for example, phenyl group), heterocyclic (for example, nitrogen-containing heterocyclic group), alkoxy group, preferably linear or Branched alkoxy groups having 1 to 20 carbon atoms (for example, methoxy, ethoxy, t-butyloxy, octyloxy, decyloxy, dodecyloxy, etc.), aryloxy groups (for example, phenoxy group), and hydrido Alkoxy group, an acyloxy group,
Preferably an alkylcarbonyloxy group, an arylcarbonyloxy group (eg, an acetooxy group, a benzoyloxy group), a carboxy, an alkyloxycarbonyl group,
Preferably a linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, preferably a phenoxycarbonyl group, an alkylthio group, preferably an acyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 20 carbon atoms. Alkylcarbonyl group, acylamino group, preferably a linear or branched alkylcarbonamide group having 1 to 20 carbon atoms, a benzenecarbamide group, a sulfonamide group, preferably a linear or branched alkylsulfonamide group having 1 to 20 carbon atoms Or a benzenesulfonamide group, a carbamoyl group, preferably having 1 to 1 carbon atoms
It represents 20 linear or branched alkylaminocarbonyl groups or phenylaminocarbonyl groups, sulfamoyl groups, preferably 1 to 20 linear or branched alkylaminosulfonyl groups or phenylaminosulfonyl groups. Next, specific examples of the compound of the cyan coupler of the present invention represented by the general formula [CA] or [CB] are described in the specification of the prior application by the present applicant, pp. 105-119. Described in the above.

 Next, the general formula [CC] will be described.

Each group represented by R _{2 to} R ₇ in the general formula [CC] includes those having a substituent.

R ₆ is preferably an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 1 to 30 carbon atoms, and R ₄ , R ₅
Are preferably a hydrogen atom and those mentioned as preferred as R ₆ .

R ₂ is directly or -NH-, -CO- or -SO _2-
Hydrogen atoms bonded to the -NH- via an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, heterocyclic group having 1 to 30 carbon atoms, -OR _8, -COR _{8, -POOR 10) 2, -POR 10)} 2, -CO 2 R 10, -SO 2 R 10
Or -SO ₂ OR ₁₀ (R ₈ , R ₉ and R ₁₀ are each R ₄ , R ₆
And R ₆ are the same as defined above, and R ₈ and R ₉ may combine to form a heterocyclic ring. Is preferred.

R ₇ is preferably an aromatic group having 6 to 30 carbon atoms, R ₇
Representative examples of the substituents include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, and a ureido Group, acyl group, acyloxy group, aliphatic oxy group,
Aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide group, aliphatic group, aliphatic oxycarbonyl group, etc. Can be. When substituted with a plurality of substituents, the plurality of substituents may be bonded to each other to form a ring, and examples thereof include a dioxymethylene group.

Representative examples of R ₃ include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, and a ureido group. An acyl group, an acyloxy group, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group, an aromatic thio group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group, an imide group, etc. I can list this R ₃
Preferably contains 0 to 30 carbon atoms. When m = 2, examples of the cyclic R ₃ include a dioxymethylene group.

When 1 is 1, R ₁ is particularly preferably -CONR ₄ R ₅ , m is preferably 0, and R ₂ is -COR ₈ , -CO directly bonded to -NH-.
_{OR 10, -SO 2 R 10,} -CONR 8 R 9, particularly preferably -SO ₂ NR ₈ R _9, the further preferred is, -COOR ₁₀ bond directly NH,
COR ₈ and —SO ₂ R ₁₀ , among which —COOR ₁₀ is most preferred.

In addition, the present invention also includes those forming a dimer or more multimer via R _{1 to} R ₃ and X.

Among the general formulas [CC], the case where l = 0 is preferable.

Specific examples of the coupler represented by the general formula [CC] are described in JP-A-60-237448, JP-A-61-153640, JP-A-61-145557, and JP-A-61-145557.
No. 62-85242, No. 48-15529, No. 50-117422, No. 52-
No. 18315, No. 52-90932, No. 53-52423, No. 54-48237
No. 54-66129, No. 55-32071, No. 55-65957,
No. 55-105226, No. 56-1938, No. 56-12643, No. 56
-27147, 56-126632, 58-95346 and U.S. Pat. No. 3,488,193, and can be synthesized by the methods described therein.

Depending on the physical properties (eg, solubility) of the coupler, an oil-in-water emulsion dispersion method using a water-insoluble high-boiling organic solvent, an alkali dispersion method of adding as an alkaline solution, and a latex dispersion may be used depending on the physical properties (eg, solubility) of the coupler. Various methods can be used, such as a solid dispersion method in which a solid is directly added as a fine solid.

The amount of the coupler to be added is usually 1.0 per mole of silver halide.
The range is from × 10 ^{-3 to} 1.0 mol, preferably from 5.0 × 10 ^{-3 to} 8.0 × 10 ^-1 mol.

Next, typical specific examples of the coupler represented by the general formula [C-C] include those described in the specification of the prior application filed by the present applicant on pages 124-142.

The cyan coupler preferably used in the present invention generally ranges from 1 × 10 ^-3 to 1 mol, preferably from 5 × 10 ^-3 to 8 × 10 ^-1 mol, per mol of silver halide.

It is an object of the present invention that at least one of the photographic constituent layers constituting the light-sensitive material of the present invention, particularly at least one of the green-sensitive emulsion layers, contains a magenta coupler represented by the following general formula [M-1]. It is preferable to achieve high efficiency.

In the formula, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. R represents a hydrogen atom or a substituent.

In the general formula [M-1], the substituent represented by R is not particularly limited, but typically, each of alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc. And a halogen atom and cycloalkenyl, alkynyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl,
Examples include aryloxycarbonyl and heterocyclic thio groups, as well as spiro compound residues and bridged hydrocarbon compound residues.

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

As the aryl group represented by R, a phenyl group is preferable.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl component and the aryl component in the alkylthio group and the arylthio group represented by R include the alkyl group and the aryl group represented by R.

The alkenyl group represented by R has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, particularly 5 carbon atoms.
To 7 are preferable, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 carbon atoms.
~ 12, especially 5-7 are preferred.

As the sulfonyl group represented by R, an alkylsulfonyl group, an annealed sulfonyl group, etc .; As the sulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, etc .; As the phosphonyl group, an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group An acylcarbonyl group such as an alkylcarbonyl group or an arylcarbonyl group; a carbamoyl group such as an alkylcarbamoyl group or an arylcarbamoyl group; a sulfamoyl group such as an alkylsulfamoyl group or an arylsulfamoyl group; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .; As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; a ureido group Such as alkyl ureido groups and aryl ureido groups; sulfamoylamino groups such as alkylsulfamoylamino groups and arylsulfamoylamino groups; and heterocyclic groups having 5 to 7 members are preferred. Is a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group or the like; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, and for example, 3,4,5,6 -Tetrahydropyranyl-2-oxy group, 1-phenyltetrazol-5-oxy group, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, a 2-pyridylthio group, a 2-benzothiathio group. Zolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group, etc .; siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutyl Proxy group or the like; succinimide imide group as a group, 3-heptadecyl succinic acid imide group, a phthalimide group, a glutarimide group and the like; spiro [3.3] As a spiro compound residue heptane -
1-yl and the like; bicyclo [2.2.1] as a bridged hydrocarbon compound residue
Heptane-1-yl, tricyclo [3.3.1.1 ^37] decane-1-yl, 7,7-dimethyl - bicyclo [2.2.1] heptane-1-yl, and the like.

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X include a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxycarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded with an N atom, alkyloxycarbonylamino, Aryloxycarbonylamino, carboxyl, (R ₁ ′ has the same meaning as R, Z ′ has the same meaning as Z, and R ₂ ′ and R ₃ ′ each represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.) And preferably a halogen atom, particularly a chlorine atom.

Examples of the nitrogen-containing heterocyclic ring formed by Z or Z ′ include a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring. Examples of the substituent that the ring may have include those described for R above. Is mentioned.

The compound represented by the general formula [MI] is more specifically represented by the following general formulas [M-II] to [M-VII].

In the general formulas [M-II] to [M-VII], R
_{1 to} R ₈ and X have the same meanings as R described above.

Among the general formulas [MI], preferred are those represented by the following general formula [M-VIII].

In the formula, R ₁ , X and Z ₁ have the same meanings as R, X and Z in the general formula [MI].

Among the magenta couplers represented by the general formulas [M-II] to [M-VII], a magenta coupler represented by the general formula [M-II] is particularly preferable.

Formula (M-I) formed by Z in the ring and Formula [M-VIII] ring has optionally substituents also formed by Z ₁ in, and Formula [M-II] - general In the formula [M-VI], R _{2 to} R ₈ represent the following general formula [M-VI
IX] is preferred.

Formula [M-IX] -R ¹ -SO ₂ -R ^{2 In the} formula, R ¹ represents an alkylene group, and R ² represents an alkyl group, a cycloalkyl group or an aryl group.

The alkylene group represented by R ¹ preferably has 2 or more carbon atoms in the straight-chain portion, more preferably 3 to 6, and may be linear or branched.

The alkyl group represented by R ² preferably have 5-6 membered.

Further, when used in positive image forming, most preferably as substituents R and R ₁ on the heterocyclic ring represented by the following general formula [M-
X].

In the formula, R ₉ , R ₁₀ and R ₁₁ have the same meanings as R described above.

Further, two of R ₉ , R ₁₀ and R ₁₁ , for example, R ₉ and R ₁₀
May be combined with each other to form a saturated or unsaturated ring (eg, cycloalkane, cycloalkene, heterocycle), and R ₁₁ may be bonded to the ring to form a bridged hydrocarbon compound residue. Good.

Among the general formulas [MX], (i) when at least two of R _{9 to} R ₁₁ are alkyl groups, (ii) at least one of R _{9 to} R ₁₁ , for example, R ₁₁ is A hydrogen atom, where the other two R ₉ and R ₁₀ combine to form a cycloalkyl with the root carbon atom.

Further, among (i), preferred are two of R _{9 to} R _11.
One is an alkyl group and the other is a hydrogen atom or an alkyl group.

When used for forming a negative image, the substituents R and R ₁ on the heterocyclic ring are most preferably represented by the following general formula [MX
I].

General formula [M-XI] R ₁₂ —CH ₂ — wherein R ₁₂ has the same meaning as R described above.

Preferred as R ₁₂ is a hydrogen atom or an alkyl group.

Representative specific examples of the magenta coupler preferably used in the present invention are described in Japanese Patent Application No.
In addition to the compounds of Nos. 1 to 77 described on page 64, among the compounds described on pages 66 to 122 of Japanese Patent Application No. 61-9791, Nos. 1 to 4,6 , 8-17,19-24,26-43,45-5
9,61-104,106-121,123-162,164-223. In addition, the magenta coupler is a journal of the chemical society (Jour
nal of the Chemical Society), Perkin I
(1977), 2047-2052, U.S. Pat.
-99437, 58-42045, 59-162548, 59-17
Nos. 1956, 60-33552, 60-43659, 60-177292
No. 60-190779, and the like.

The magenta coupler is usually used in an amount of 1 per mole of silver halide.
It can be used in the range of × 10 ^-3 to 1 mol, preferably 1 × 10 ^-2 to 8 × 10 ^-1 mol.

The magenta dye-forming coupler preferably used in the present invention can be represented by the following general formula [M-XII].

Ar: a phenyl group, particularly a substituted phenyl group.

As the substituent, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group,
A cyano group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfonamide group, an acylamino group, and Ar
The phenyl group represented by may have two or more substituents.

 Specific examples of the substituent are described below.

Halogen atom: chlorine, bromine, fluorine Alkyl group: methyl group, ethyl group, iso-propyl group, butyl group, t-butyl group, t-pentyl group, etc., and particularly preferably an alkyl group having 1 to 5 carbon atoms. .

Alkoxy group: a methoxy group, an ethoxy group, a butoxy group, a sec-butoxy group, an iso-pentyloxy group and the like, and an alkoxy group having 1 to 5 carbon atoms is particularly preferable.

Aryloxy group: a phenoxy group, β-naphthoxy group and the like, and the aryl portion may further have the same substituent as that of the phenyl group represented by Ar.

Alkoxycarbonyl group: a carbonyl group having the above-mentioned alkoxy group, and having 1 to 1 carbon atoms in the alkyl moiety such as a methoxycarbonyl group and a pentyloxycarbonyl group.
Five are preferred.

Carbamoyl group: an alkylcarbamoyl group such as a carbamoyl group and a dimethylcarbamoyl group.

Sulfamoyl group: an alkylsulfamoyl group such as a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, and an ethylsulfamoyl group.

Sulfonyl group: alkylsulfonyl group such as methanesulfonyl group, ethanesulfonyl group and butanesulfonyl group;
Arylsulfonyl group.

Sulfonamide group: alkylsulfonamide group such as methanesulfonamide group and toluenesulfonamide group, and arylsulfonamide group.

Acylamino group: an acetamino group, a bivaloylamino group, a benzamide group and the like.

Particularly preferred is a halogen atom, and among them, chlorine is most preferred.

Y: represents a group which is released when a dye is formed by coupling with an oxidized form of a p-phenylenediamine color developing agent.

Specifically, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, (Z is a nitrogen atom together with a carbon atom, an oxygen atom, a nitrogen atom,
Represents a group of atoms required to form a 5- or 6-membered ring with atoms selected from sulfur atoms. The following is a specific example.

 Halogen atom: chlorine, bromine, fluorine.

Alkoxy group: ethoxy group, benzyloxy group, methoxyethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group and the like.

Aryloxy group: phenoxy group, 4-methoxyphenoxy group, 4-nitrophenoxy group and the like.

Acyloxy group: acetoxy group, myristoyloxy group, benzoyloxy group and the like.

Arylthio group: phenylthio group, 2-butoxy-5
-Octylphenylthio group, 2,5-dihexyloxycyphenylthio group and the like.

Alkylthio group: methylthio, octylthio, hexadecylthio, benzylthio, 2- (diethylamino) ethylthio, ethoxycarbonylmethylthio, phenoxyethylthio, and the like.

Pyrazolyl group, imidazolyl group, triazole group, tetrazolyl group, etc. When R is an acylamino group, examples thereof include an acetamido group, an isobutylamino group, a benzamide group,
[Α- (2,4-di-tert-amylphenoxy) butylamide] benzamide group, 3- [α- (2,4-di-tert-
Amylphenoxy) acetamide] benzamide group, 3
-[Α (3-pentadecylphenoxy) butyramide]
Benzamide group, α- (2,4-di-tert-amylphenoxy) butylamide group, α- (3-pentadecylphenoxy) butylamide group, hexadecaneamide group, isostearylamino group, 3- (3-octadezenylsuccinne Imido) benzamide group or bivaloylamino group, and when R is an anilino group, examples thereof include anilino group, 2-chloroanilino group, 2,4-dichloroanilino group, 2,5-dichloroanilino group, and 2 , 4-Dichloroanilino group, 2,5-dichloroanilino group, 2,4,5-trichloroanilino group, 2-chloro-5- (3-octadecenylsuccinimido) anilino group, 2-chloro −5- [α- (3-
tert-butyl-4-hydroxy) tetradecaneamide)
Anilino group, 2-chloro-5-tetradecyloxycarbonylanilino group, 2-chloro-5- (N-tetradecylsulfamoyl) anilino group, 2,4-dichloro-5-
Tetradecyloxyanilino group, 2,4-chloro-5-
(Tetradecyloxycarbonylamino) anilino group,
2-chloro-5-octadecylthioanilino group or 2-
Chloro-5- (N-tetradecylcarbamoyl) anilino group and the like. When R is a ureido group, an example is 3-{(2,4-
Di-tert-aminophenoxy) acetamide｝ phenylureido group, phenylureido group, methylureido group,
Examples include an octadecylureido group, a 3-tetradecanamidophenylureido group, and an N, N-dioctylureido group.

Among the compounds represented by the general formula [M-XII], a particularly preferred compound is represented by the general formula [M-XIII].

In the formula, Y and Ar represent the same meaning as in the general formulas [M to XII].

X: represents a halogen atom, an alkoxy group or an alkyl group.

 Specific examples are given below.

Halogen atom: chlorine, bromine, fluorine Alkoxy group: An alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group, a butoxy group, a sec-butoxy group, an i-pentyloxy group is preferable.

Alkyl group: An alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a butyl group, a t-butyl group, a t-pentyl group, is preferred.

Particularly preferred are halogen atoms, and chlorine is particularly preferred.

R ₁ represents a group that can be substituted on a benzene ring, and n is 1 or 2
Represents When n is 2, R ₁ may be the same or different.

Examples of the group that can be substituted on the benzene ring represented by R ₁ include a halogen atom, R′—, R′O—, Is mentioned.

R ', R "and R may be the same and different and each represent a hydrogen atom or an alkyl group, an alkenyl group or an aryl group each of which may have a substituent. Of these, R'CONH-, R'SO ₂ NH-, It is.

Specific examples of these magenta couplers preferably used in the present invention are those described on page 42 to page 51 of Japanese Patent Application No. 60-131590 and pages 39 to 51 of Japanese Patent Application No. 59-172154.
The couplers described on page 46 can be mentioned, and these couplers are described in JP-A-56-38043, JP-A-57-14837, and JP-A-57-2040.
Compounds can be easily synthesized according to the methods described in JP-A Nos. 36 and 58-14833.

The addition amount of these magenta couplers is preferably 0.005 to 2 mol per mol of silver halide, more preferably 0.01 to 2 mol.
１1 mol.

The cyan coupler or magenta coupler may be used alone or in combination of two or more, and may be used in combination with one or more of other types of cyan coupler or magenta coupler.

When the light-sensitive material of the present invention has two or more photosensitive emulsion layers having different sensitivities, a cyan coupler or a magenta coupler preferably used in the present invention may be applied to one or more layers.

The silver halide emulsion that can be used in the present invention is preferably a lithographic silver halide emulsion.
Any of silver halides such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide and silver chloroiodobromide may be used. As the protective colloid of these silver halides, in addition to natural products such as gelatin, various products obtained by synthesis can be used.

The silver halide emulsion may contain usual photographic additives such as a stabilizer, a sensitizer, a hardener, a sensitizing dye, and a surfactant.

As the photosensitive material used in the present invention, any of a color negative film, a color paper, a color reversal film, a color reversal paper and the like can be used.

[Effects of the Invention] According to the present invention, there is provided a method for processing a photosensitive material in which a bleaching solution is processed immediately after color development, and then a processing solution having a fixing ability is used. In addition, the present invention provides a processing method in which a processing solution having a fixing ability, which is generated by mixing a bleaching fog, poor color reversal, and a bleaching solution into a processing solution having a fixing ability, has improved storage stability.

〔Example〕

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

In Example 1 all examples, the amount of silver halide photographic light-sensitive material is particularly shows the g per 1 m ² unless otherwise noted.
Further, silver halide and colloidal silver are shown in terms of silver.

On a cellulose triacetate film support, an ultra-sensitive multi-layer color photographic light-sensitive material comprising the following layers was prepared.

First layer: Anti-halation layer Black colloidal silver 0.2 Gelatin 1.7 Ultraviolet absorber (UV-1) 0.3 Colored coupler (CM-1) 0.2 Oil for dispersing ultraviolet absorber (oil-1) 0.15 Ultraviolet absorption Oil for dispersing agent (oil-2) ... 0.15 Oil for dispersing colored coupler (oil-3) ... 0.2 Second layer: Intermediate layer Gelatin ... 1.2 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion ( Em-1) 1.0 Silver iodobromide emulsion (Em-2) 0.5 Gelatin 1.3 1.3 Sensitizing dye (S-1) 0.5 x ^10-4 (mol / silver 1 mol) Sensitizing dye (S-2) 2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 2 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C′-1) 0.07 Cyan coupler (C′-) 2) 0.3 Cyan coupler (C'-4) 0.3 Colored cyan coupler (CC-1) 0.07 DIR compound (D-1) 0.005 ( '-1), (C'-2), (C'-4),
Oil for dispersing (CC-1) and (D-1) (oil-1) ... 0.2 Fourth layer: Intermediate layer Gelatin ... 0.8 Fifth layer: First green-sensitive emulsion layer Silver iodobromide emulsion (Em-1) ) 1.0 Silver iodobromide emulsion (Em-2) 0.5 Gelatin 1.4 Sensitizing dye (S-4) 1.8 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-5) 1.3x 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-6) ... 9.2 × 10 ^-5 (mol / silver 1 mol) Sensitizing dye (S-7) ... 6.8 × 10 ^-5 (mol / silver 1 mol) Mol) Sensitizing dye (S-8) ... 6.2 x ^10-4 (mol / silver 1 mol) Magenta coupler (M'-1) 0.15 Colored magenta coupler (CM-1) 0.08 (M'-1), Oil for dispersion of (CM-1) (oi
l-3) 0.23 6th layer: Intermediate layer Gelatin 0.8 0.8 Color contamination inhibitor (SC-1) 0.05 Oil for dispersing (SC-1) (oil-3) 0.05 0.05 7th layer: 1st blue sensitivity Emulsion layer Silver iodobromide emulsion (Em-1) 0.8 Gelatin 0.6 Sensitizing dye (S-9) 3 x ^10-4 (mole / silver 1 mol) Sensitizing dye (S-10) 1 x 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y'-1) ... 0.3 Oil for dispersing (Y'-1) (oil-3) ... 0.3 8th layer: Intermediate layer Gelatin ... 0.8 Color stain inhibitor ( SC-1) ... 0.05 Dispersion oil of (SC-1) (oil-3) ... 0.05 9th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Em-1) ... 1.0 Silver iodobromide emulsion ( Em-3) 2.0 2.0 fine-grain AgX emulsion (average particle size 0.08 μm) AgI = 2 mol% silver iodobromide 0.5 Gelatin 2.4 sensitizing dye (S-1) 0.2 × 10 ^-4 (mol / silver 1) mole) sensitizing dye (S-2) ... 1.0 × 10 -4 ( mol / 1 mol) Cyan coupler (C'-1) ... 0.2 Cyan coupler (C'-3) ... 0.05 Cyan coupler (C'-4) ... 0.10 Color stain inhibitor (SC-1) ... 0.05 (C'-1) , (C'-3), (C'-4),
Oil for dispersing (SC-1) (oil-1) ... 0.4 10th layer: intermediate layer Gelatin ... 0.8 Color stain inhibitor (SC-1) ... 0.07 Colored magenta coupler (CM-1) ... 0.04 (SC-1) ), Dispersion oil of (CM-1)
-3) 0.25 11th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0.8 Silver iodobromide emulsion (Em-3) 1.6 Gelatin 1.6 sensitizing dye (S-4) 6.8 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-5) 6.7 × 10 ^-5 (mol / silver 1 mol) Sensitizing dye (S-6) 2.1 × 10 ^-6 (mol / Silver 1 mol) Magenta coupler (M'-1) ... 0.2 Colored magenta coupler (CM-1) ... 0.02 Oil for dispersing (M'-1), (CM-1) (oi)
l-4) 0.2 Layer 12: Intermediate layer Fine particle AgX emulsion (average particle size 0.08 μm) AgI = 2 mol% silver bromide 0.3 Gelatin 0.8 Color stain inhibitor (SC-1) 0.05 (SC- 1) Dispersion oil (oil-3) ... 0.4 13th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Em-1) ... 0.7 Silver iodobromide emulsion (Em-4) ... 1.4 Fine grain AgX emulsion (Average particle size: 0.08 μm) AgI = 2 mol% silver iodobromide: 0.1 fine-grain AgX emulsion (average particle size: 0.3 μm) AgI = 2 mol% silver iodobromide: 0.1 Gelatin: 2.1 Sensitizing dye (S- 10) 0.4 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y'-1) 0.8 (Y'- 1) Dispersion oil (oil-3) ... 0.8 14th layer: 1st protective layer Gelatin ... 1.5 UV absorber (UV-1) ... 0.1 UV absorber (UV-2) ... 0.1 Formalin scavenger (HS-1) …… 0.5 formalin Kabenja (HS-2) ... 0.2 dispersion oil of the ultraviolet absorbent (oil-1) ... 0.1
Oil for dispersing ultraviolet absorber (oil-2) ... 0.1 15th layer: 2nd protective layer Gelatin ... 0.6 Alkali-soluble matting agent (average particle size 2 m) ... 0.12 Polymethyl methacrylate (average particle size 3 m) ... 0.02 Sliding agent (WAX-1) ... 0.04 Charge control agent (W-1) 0.004 In addition to the above composition, each layer has a coating aid Su-1, dispersion aids Su-2 and Su-3, and a hardening layer. Agents H-1 and H-2, stabilizer St-1, and antifoggants AF-1 and AF-2 were added.

Em-1 Average grain size 0.8 μm, average silver iodide content 8.0%, monodisperse surface low silver iodide content emulsion Em-2 Average grain size 0.40 μm, average silver iodide content 7.0%, monodisperse Surface low silver iodide containing emulsion Em-3 average grain size 1.6 μm, average silver iodide content 6.4%, monodisperse surface low silver iodide containing emulsion Em-4 average grain size 2.0 μm, average Silver iodide content 7.0%, monodisperse surface low silver iodide content emulsion The photosensitive material thus prepared was subjected to wedge exposure using white light, and then subjected to the following development processing.

Experimental processing Processing step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 45 seconds 37 ° C Fixed 90 seconds 37 ° C Stabilized 60 seconds 37 ° C Drying 60 seconds 70 ° C The processing solution composition used is as follows: It is.

Color developing solution Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 4 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β -Hydroxyethyl) aniline sulfate 4.8 g Potassium hydroxide 1.2 g Add water to make 1 and adjust to pH 10.06 with potassium hydroxide or 50% sulfuric acid.

Bleaching solution Bleaching agent listed in Table 1 Ammonium bromide 150 g Add water to make 1 and adjust to pH 5.5 with aqueous ammonia or glacial acetic acid.

Fixing solution Ammonium thiosulfate 250 g Ammonium sulfite 20 g Imidazole (buffer of the present invention) 20 g Add water to 1 to adjust pH to 1 using acetic acid and aqueous ammonia.
Adjust to 7.0.

Stabilizing solution formaldehyde (37% solution) 2 ml 5-chloro-2-methyl-4-isothiazoline-3-
ON 0.05g Emulgen 810 1ml Formaldehyde bisulfite sodium adduct 2g Add water to make 1 and add ammonia water and 50% sulfuric acid
Adjust to pH 7.0.

The developed sample was measured with a PDA-65A optical densitometer (manufactured by Konica Corporation) to measure the minimum densities of yellow, magenta, and cyan with blue light, green light, and red light, respectively, as bleaching fog characteristics. The red density of the maximum density portion was measured as a characteristic of poor color reproduction of cyan.
Table 1 shows the above results.

As shown in Table 1, the method of the present invention in which a bleaching solution containing a compound of the general formula [A] as a bleaching agent is processed within 90 seconds and then treated with a processing solution having a fixing ability according to the present invention is used as a bleaching agent. Using only a ferric complex salt of ethylenediaminetetraacetic acid,
It can be seen that both the bleaching fog and the poor recoloring of cyan are better than the prior art in which the processing time with the bleaching solution exceeds 90 seconds.

Example 2 As a fixing solution, a buffer was used as shown in Table 2, and 50 ml of a bleaching solution was added to the fixing solution, and the fixing solution was stored at 38 ° C. for 2 weeks (the pH of the solution was as shown in Table 2). Other than that, an experiment similar to Experiment No. 11 of Example 1 was performed. The preservability of the fixing solution was determined by visually observing the state of the fixing solution after storage. The criteria are as follows.

…: No abnormality.

Δ: Slight turbidity is observed.

X: Suspended matters or precipitates are clearly observed.

 Table 2 shows the results.

From Table 2, it can be seen that in the bleaching treatment using the bleaching solution of the present invention within 90 seconds, the buffer of the present invention is used as the buffer of the fixing solution, and the pH of the fixing solution is within the range of the present invention. It can be seen that both the bleaching fog and the poor recoloring of cyan and the preservability of the bleaching solution when the bleaching solution is mixed in the fixing solution can be achieved well.

Example 3 An experiment was conducted in the same manner as in Experiment No. 15 of Example 2, except that the processing time with the bleaching solution and the buffer and pH of the fixing solution were as shown in Table 3. Table 3 shows the results.

From Table 3, when the bleaching agent represented by the general formula [A] is used as the bleaching agent of the bleaching solution, the processing time of the bleaching solution is 90 hours.
Within seconds, when the buffer of the present invention is used as a buffer for the fixing solution, and the pH of the fixing solution is adjusted to 6.0 to 8.5, the bleaching fog, poor recoloring of cyan, and the bleaching solution are mixed into the fixing solution. It can be seen that all of the three preservatives of the bleaching solution were good.

Example 4 The same experiment as in No. 19 of Example 2 was performed except that the buffer of the fixing solution was as shown in Table 4. Table 4 shows the results.

Table 4 shows that various buffers according to the present invention exhibit the effects of the present invention.

Example 5 The same experiment as in Experiment No. 18 of Example 2 was performed except that the amount of the buffer of the present invention was changed as shown in Table 5. The results are shown in Table 5 below.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-102559 (JP, A) JP-A-1-206340 (JP, A) JP-A-62-123463 (JP, A) JP-A-62-123463 123460 (JP, A) JP-A-62-222252 (JP, A) JP-A-62-166346 (JP, A) JP-A-62-89964 (JP, A) (58) Fields investigated (Int. ⁶ , DB name) G03C 7/42

Claims (1)

(57) [Claims] Claims: 1. Immediately after color development, processing with a bleaching solution is performed.
In a method for processing a silver halide color photographic light-sensitive material for photography, which is subsequently processed with a fixing solution, the bleaching solution contains a ferric complex salt of a compound represented by the following general formula [A], and the processing time with the bleaching solution is as follows: Is 90 seconds or less, and the fixing solution is selected from buffers such as carbonic acid, phosphoric acid, boric acid, citric acid, imidazole, triethanolamine, ethylenediamine and salts thereof having a buffering capacity at pH 6.0 to 8.5. Containing at least one from 0.01 to 0.5 mol /
A method for processing a silver halide color photographic light-sensitive material, wherein H is 6.0 to 8.5. Wherein A _{1 to} A ₄ may be the same or different,
CH ₂ OH, -COOM, represent a -PO ₃ M ₁ M _2. M, M ₁ and M ₂ are each a hydrogen atom, a sodium atom, a potassium atom or an ammonium group. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. ]