JPH0284641A - Method for processing silver halide color photographic sensitive material for photography - Google Patents

Abstract

PURPOSE:To enable the rapid bleach-processing of the subject material, and to suppress the generation of a bleach-fog, a faulty recoloring of the material and the deterioration of a processing solution due to the contamination of a bleaching solution by specifying a ferric complex salt contd. in a bleaching solution, a processing time with the bleaching solution and pH of the processing solution having fixing ability, respectively. CONSTITUTION:The ferric complex salt of a compd. shown by formula I is incorporated in the bleaching solution, and the processing time of the material with the bleaching solution is specified to <=90sec. The processing solution having the fixture ability is specified to pH of 6.0-8.5 in the processing solution. In formula I, A1-A4 are the same or the different with each other, and are each -CH2OH, -COOM or -PO3M1M2 group, M-M2 are each hydrogen, sodium or potassium atom or ammonium group, X is 3-6 C alkylene group. Thus, the processing of the photosensitive material with the bleaching solution is rapidly performed, and the generation of the bleach fogging, the faulty recoloring of the material and the shelf life of the processing solution are improved.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for processing a silver halide color photographic light-sensitive material for photography (hereinafter also simply referred to as a "photosensitive material"), and more particularly, to This technology relates to bleaching and fixing processes suitable for color printing, and can be suitably used for high-sensitivity light-sensitive materials containing a large amount of silver.

[Background of the invention]

Processing of light-sensitive materials basically consists of two steps: color development and desilvering, and desilvering consists of bleaching and fixing steps or bleach-fixing steps. In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps.

The processing solution with bleaching ability used in the desilvering process of photosensitive materials contains red blood salt, red blood salt, etc. as an oxidizing agent to bleach the image silver.
Inorganic oxidizing agents such as dichromates are widely used.

However, several serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents and having bleaching ability. For example, red blood salt and dichromate are relatively superior in terms of bleaching blades for image silver, but they can decompose when exposed to light and generate cyanide ions and hexavalent chromium ions that are harmful to the human body, causing pollution. It has properties that are unfavorable in terms of prevention. Furthermore, treatment liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse them without discarding the waste liquid after treatment.

On the other hand, metal complex salts of organic acids such as aminopolycarboxylic acid metal complex salts have been used as oxidizing agents, as they have fewer pollution problems and meet the demands of speeding up and simplifying treatment, and enabling recycling of waste liquid. Treatment liquids have come into use. However, processing solutions using metal complex salts of organic acids have a slow oxidizing power, so they have the disadvantage that the bleaching rate (oxidation rate) of image silver (metallic silver) formed in the development process is slow. .

For example, iron ethylenediaminetetraacetate (II
I) Complex salts have been put to practical use in some areas as bleaching solutions and bleach-fixing solutions, but they can also be used in high-sensitivity silver halide color photographic materials containing silver bromide and silver iodobromide emulsions, especially as silver halide. Color paper for photography, color negative film for photography, and color reversal film containing silver iodide and a high amount of silver have the disadvantage that bleaching blades are insufficient and the bleaching process takes a long time.

In addition, in the development processing method in which a large amount of photosensitive material is continuously processed using an automatic processor, etc., in order to avoid deterioration of the performance of the bleaching solution due to changes in the concentration of the components, it is necessary to keep the components of the processing solution within a constant concentration range. A means is necessary.

In recent years, as such a method, a so-called concentrated low replenishment method has been proposed, in which the replenisher is concentrated and refilled in small quantities, and a method in which a regenerating agent is added to the overflow fluid and used again as a replenisher has been proposed in recent years from the viewpoint of economy and pollution. It's coming.

In particular, in a bleaching solution, an organic acid ferrous complex salt produced by bleaching developed silver, such as an ethylenediaminetetraacetate iron (FF) complex salt, is converted into an ethylenediaminetetraacetate iron (III) complex salt, that is, an organic acid ferric complex salt, by aeration. A method has been put into practical use in which the solution is oxidized back to the original state, and a regenerating agent is added to supplement the missing components, and the solution is used again as a replenisher.

However, in recent years, so-called compact laboratories (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. There is a strong need to reduce the installation area of the machine, and recycling processing is not desirable because it requires complicated labor and management, and also requires processing space.

Therefore, it is preferable to use a concentrated low replenishment method that performs low replenishment without performing regeneration processing, but if the amount of replenishment of the bleaching solution is extremely reduced, the concentration of color developer components brought into the bleaching solution will increase.
Furthermore, it becomes more susceptible to the effects of concentration due to evaporation, and the accumulation of color developer components increases. As described above, when the concentration of the color developer components in the bleaching solution increases, the mixing ratio of reducing components such as color developing agents and sulfites increases, which inhibits the bleaching reaction and tends to cause failures called desilvering failures. Become. In order to overcome these shortcomings, Research Disclosure ar-(Research Disclosure
re) No. 24023 and JP-A-62-222252
The specific aminopolycarboxylic acid No. 2 described in No.
Techniques using iron complex salts and mixtures thereof have been proposed.

However, it has been found that these techniques have various drawbacks. For example, the ferric complex salt of 1,3-diaminopropanetetraacetic acid described in the above-mentioned literature or patent publication is used to bleach the bleaching blade when bleaching high-sensitivity light-sensitive materials containing a large amount of silver over a long period of time. will occur. In other words, when bleaching or bleach-fixing low-sensitivity light-sensitive materials based on silver chlorobromide emulsions, using these as bleaching agents can achieve the desired purpose. High-sensitivity color-sensitized light-sensitive materials that are mainly composed of silver iodide or silver iodobromide emulsions, especially color negative light-sensitive materials for ultra-high-sensitivity photography (for example, ASA sensitivity 400 to 3200) that use high-silver emulsions. When processing, there is a problem in that the bleaching blade burrs. In particular, this drawback becomes even more pronounced when the amount of bleach solution replenishment is reduced. Moreover, this tendency is observed when the concentration of the color developing agent used in the color development treatment, which is a pre-bleaching process, is 1.5X.
It was found that when the amount is 10-2 mol or more, the effect becomes more pronounced.

The present inventors have found that a bleaching time of 90 seconds or less is desirable because this bleaching edge burr increases with bleaching time. It has also been found that there is a problem in that the colors are not sufficiently developed, resulting in poor color recovery.

Furthermore, another problem when using 1,3-diaminopropanetetraacetic acid ferric complex salt as a bleaching agent is that when the bleaching solution is carried into the processing solution that has fixing ability in the next processing step, the processing There is a problem in that the storage stability of the liquid is greatly deteriorated.

Therefore, there is a need for the development of a technology that can process photosensitive materials with high sensitivity and high silver content without causing bleaching edge blur or defective color restoration, and without deteriorating the storage stability of the fixer when the bleach mixes with the fixer. It is being

[Purpose of the invention]

The purpose of the present invention is to speed up the bleaching process and eliminate bleaching edge blur and poor color restoration in a method for processing photosensitive materials in which a bleaching solution is immediately applied after color development, followed by a processing solution that has fixing ability. Another object of the present invention is to provide a method for processing a photosensitive material in which deterioration of a processing solution having fixing ability due to contamination with a bleaching solution is improved.

[Structure of the invention]

The processing method of the present invention that achieves the above object includes, after color development,
In a method for processing a photographic light-sensitive material, which is immediately treated with a bleaching solution and subsequently treated with a processing solution having fixing ability, the bleaching solution contains a ferric complex salt of a compound represented by the following formula [A], and the processing time with the bleaching solution is 90 seconds or less, and the processing solution having the fixing ability has a pH of 6.0 to 6.0.
Contains a buffer with a buffering capacity of 8.5 and pl (6,0~
It is characterized by being 8.5.

General formula (A) (A-1) In general formula (A), A, , A2, As and A.

may be the same or different < , -CH! O
H.

-COOM or -P03M, representing Ml. M, M
+ and M each represent a hydrogen atom, a sodium atom, a potassium atom or an ammonium group. X has 3 to 6 carbon atoms
represents a substituted or unsubstituted alkylene group.

[Specific structure of the invention]

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

In general formula (A), the substituted or unsubstituted alkylene group having 3 to 6 carbon atoms represented by X is, for example, propylene group, butylene group, trimethylene group, tetramethylene group, pentamethylene group, etc. Examples include substituted groups.

Below, the compound represented by the above general formula [A] is
Eyes and uneven corners (A-2) (A-3) (A-4) (A-5) (A-6) (A-7) (A-8) and these (A-1) ~ (A-8) sodium salt, potassium salt or ammonium salt.

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

Among the above compound examples, those particularly preferably used in the present invention are (A-1), (A-2), and (A-4).
), (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 N2 bleaching solution, more preferably o, oi mol to 0.3 mol, particularly preferably 0.05 mol. ~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 its salt (
salts of ammonium, sodium, potassium, triethanolamine, etc.) (A'-2) l'lance-1,2-cyclohexanediaminetetraacetic acid or its salt (〃) (A'-3) Dihydroxyethylglycinate or its salt (〃) (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) (A'-9) (A'-10) (A'-11) (A'-12) (A'-13) (A'-14) (A'-15) (A' -16) (A'-17) Salt (〃) Ethylenediaminediorthohydroxyphenylacetic acid or its salt (〃) Hydroxyethylethylenediaminetriacetic acid or its salt (//) Ethylenediaminedipropionic acid or its salt (//) Ethylenediamine dipropionic acid or its salt Acetic acid or its salts (〃) Glycol ether diamine tetraacetic acid or its salts (〃) Hydroxyethyliminodiacetic acid or its salts (〃) Nitrilotriacetic acid or its salts (〃) Nitrilotripropion diacetate or sono salt (〃) Triethylenetetramine Hexaacetic acid or its salt (〃) Ethylenediamineditetrapropionic acid or its salt (〃) The above-mentioned compounds can be mentioned, but of course the compounds are not limited to these exemplified compounds.

In these compounds, special 4: A'-1, A'-2, A'-
7 and A'-12 are preferred.

These aminopolycarboxylic acid iron (m) complex salts may be used in the form of complex salts, or iron (II) salts, such as ferric sulfate,
An iron (III) ion complex salt may be formed in a solution using ferric chloride, ferric acetate, ferric ammonium sulfate, ferric phosphate, etc., and an aminopolycarboxylic acid or a salt thereof. When used in the form of a complex salt, one type of complex salt or two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and an aminopolycarboxylic acid, one or more types of ferric salts may be used. Furthermore, one type or two or more types of aminopolycarboxylic acids may be used. In any case, the aminopolycarboxylic acid may be used in excess of the amount required to form the iron (III) complex salt.
Alternatively, it may be used as a triethanolamine salt, or two or more of these may be used in combination.

The bleaching solution containing the iron (I[[) ion complex described above may also contain metal ion complex salts other than iron, such as cobalt, copper, nickel, and zinc.

The bleaching solution of the present invention can contain a buffer.

Preferably used buffering agents include the following formula (1),
C11) or an organic compound represented by (II), nitrogen,
Mention may be made of inorganic compounds such as compounds containing at least 1 phosphorus or boron atoms.

General formula (1,) -COOH In the formula, A represents a hydrogen atom or an organic compound group.

- Formula (II) B-PO3H.

In the formula, B represents a hydrogen 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 C1D and E is an organic compound group.

Next, specific examples of buffers preferably used in the present invention will be given.

Preferred compounds as fatty acids are acrylic acid, adipic acid, acetylene dicarboxylic acid, acetoacetic acid, azelaic acid, isocrotonic acid, isopropylmalonic acid, isobutyric acid, itaconic acid, isovaleric acid, ethylmalonic acid, caproic acid, formic acid, and valeric acid. , citric acid, glycolic acid, glutaric acid, crotonic acid, chlorfumaric acid, α-chloropropionic acid, curconic acid, glyceric acid, β-chloropropionic acid, succinic acid, cyanacetic acid, diethyl acetic acid, diethylmalonic acid, dichloroacetic acid, Citraconic acid, dimethylmalonic acid, oxalic acid, d-tartaric acid, eso-tartaric acid, trichlorolactic acid, tricarballylic acid, trimethylacetic acid, lactic acid, vinylacetic acid, pimelic acid, pyrotartaric acid, grape acid, fumaric acid, propionic acid, propyl Examples include malonic acid, maleic acid, malonic acid, mesaconic acid, methylmalonic acid, monochloroacetic acid, n-butyric acid, malic acid, aspartic acid, DL-alanine, glutamic acid, and 3,3-dimethyl glutaric acid.

Among the acids having a cyclic structure, preferred compounds include ascorbic acid, atrobeic acid, allocinnamic acid, benzoic acid, isophthalic acid, oxybenzoic acid (11-%I)-% chlorobenzoic acid (0-1■-1p- ), chlorphenylacetic acid (o-1m
-1p-), 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-1cis-),
Dichloropropane-1,1-dicarboxylic acid, cyclopropane-1,2-dicarboxylic acid (trans-1cis-
), cyclohexane-1,1-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid (trans-1CIS
-)% cyclohexyl acetic acid, cyclobencune=l.

l-dicarboxylic acid, 3.5-dinitrobenzoic acid, 2.4
-dinitrophenoldiphenylic acid, sulfanilic acid,
Terephthalic acid, toluic acid Co-1-1p-), naphthoic acid (α-1β-), nicotinic acid, nitroanisole (o
-1m-1p-), nitrobenzoic acid, nitrophenylacetic acid (0-1■-1p-), p-nitrophenethol, pyromucic acid, uric acid, hippuric acid, barbituric acid, picolinic acid,
Pooruric acid, phenylacetic acid, phenyl acid, phthalic acid, fluorobenzoic acid (0-1-1p-), bromobenzoic acid (
0-1■-1p-), hexahydrobenzoic acid, benzylic acid, d(1-phthalic acid, mesitylenic acid, methoxybenzoic acid (0-1s-1p-), methoxycinnamic acid (0-1-
1, p-), p-methoxyphenylacetic acid, gallic acid, aminobenzoic acid (0-1 p-), and the like.

Preferred amine compounds include isoamylamine, isobutylamine, isopropylamine, ethylamine, ethylenediamine, diisoamylamine, diisobutylamine, diethylamine, diethylenetriamine, dipropylamine, dimethylamine, tetraethylenepentamine, tetramethylenediamine, triethylamine, trimethylamine, trimethyldiamine, spade
Butylamine, 5ec-butylamine, tert-butylamine, ■-propylamine, pentamethylenediamine, hexamethylenetetramine, quinoline, 0-toluidine, aminobenzenesulfonic acid (O-, Kaku-1p-)
, N-methylbenzylamine, methylbenzylamine (
o-1m・, p・), 2-methylpiperidine, N-methoxybenzylamine, methoxybenzylamine (0-1
Examples include ring-1p.), 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, and polymetaphosphoric acid.

Other preferred organic compounds include N-(2-acetamido)iminodiacetic acid, N-(2-acetamido)
-aminoethanesulfonic acid, bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane, 2-(
N-morpholino)ethanesulfonic acid, 3-(N-morpholino)-2-hydroxypropanesulfonic acid, piperazine-N,N'-bis(2-ethanesulfonic acid), ethylenediaminediacetic acid, ethylenediamine-2-propionic acid, β-Aminoethyliminodiacetic acid, etc., and others.
Preferred organic phosphoric acids include aminomethylphosphonic acid-N,N-diacetic acid, 2-phosphonoethyliminodiacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, and the following (P -1) (P-2) (p-9) (p-10) (P-3) (P-4) (P-11) (P-12) (p-5) (p-6) (P -13) (p -14) (P-7) CP-8> (P-15) (P-16) (P-17) (P -18) (P -24) (p-19) (P - 20) c p -25) (P-26) (P -21) (P -22) (P -27) (P -28) (P -23) (P -29) (P -30) (P - 31) (P-32) CH,C00H (P-33) (P-34) Among the above compounds, fatty acids, acids with a cyclic structure, amine compounds, and inorganic salts are more preferred, and fatty acids and amines are particularly preferred. Preferably, the compounds are 1, N.

Incidentally, among organic acids, acetic acid is slightly less effective than the above-mentioned compounds.

However, Amitsubo 1-nocarboxylic acid contained as a bleaching agent (
or phosphonic) acid ferric complex salt at least 40% (mol ratio), preferably at least 50% (molar ratio)2! l (in the case of a ferric complex salt of the compound represented by the general formula [A], or when the ferric complex salt of the compound represented by the general formula [A] is 0.2
If it is mol/Q or more, 0.5~
It has been found that a range of 3 mol/Q, preferably a range of 0.8 to 21/12, is extremely effective for liquid stability (floating matter prevention effect).

The pH of the bleaching solution of the present invention is in the range of 3 to 7, and the pH range of 4 to 6 is particularly preferred from the viewpoint of the effects of the present invention. The most preferred range is pH 4.5 to 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 a temperature of 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 111% of the photosensitive material.
20a to 500@12 per ffi, particularly preferably 3 (m2 to 350m12), even more particularly preferably 40a12 to 300+aQ, most preferably 50+*12 to 250sff.

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

The bleaching solution of the present invention may also contain various optical brighteners, antifoaming agents, or surfactants.

In the present invention, if the treatment time with the bleaching solution exceeds 90 seconds, there is a strong tendency for bleaching blade blur to occur.

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

A so-called fixing agent is essential to the processing solution (fixing solution and bleach-fixing solution) having fixing ability according to the present invention.

As fixing agents, compounds that react with silver halides to form complex salts in aqueous solution, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate are used. Examples include thiocyanates, thioureas, thioethers, and halides such as iodides.

The processing liquid having fixing ability according to the present invention is %l1lH6-0
Contains a buffer having a buffering capacity of ~8.5 (hereinafter referred to as "buffer of the present invention"). In the definition of the buffer of the present invention, the term "buffer having a buffering ability at rpH 6.0 to 8.5" means increasing the buffering ability to 98 of a processing solution having a fixing ability with a pH of 6.0 to 8.5. A buffering agent that has the effect of

The buffering agent of the present invention can be selected from compounds having a pKa [(at 25° C., ionic strength 0)] in the range of 5.0 to 9.5. Specific examples of compounds are listed below.

Malic acid, pyridine, p-1' luidine, heptalic acid, piperazine, succinic acid, malonic acid, uric acid, tetraethylethylenediamine, 2-(N-morpholino)ethanesulfonic acid, maleic acid, 3,3-dimethyl geltaric acid , carbonic acid, 4-hydroxymethylimidazole, citric acid, northophosphorous acid, N-(2-acetamido)iminodiacetic acid, Virolin 1m, 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-ethane Sulfonic acid, N-ethylmorpholine, triethanolamine, hepnotris-2-hydroxyethylimino-tris(hydroxymethyl)methane,
5.5-diethylbarbital acid, tris(tris(hydroxymethyl)aminomethane, l,4-bis(3-sulfopropyl)piperazine, glycylglycine, 2.5
-dimethylimidazole, tris(hydroxyethyl)
Methylaminopropanesulfonic acid, tetrakis-(2-
Hydroxyethyl) ethylenediamine, N-methyljetanolamine, 2-amino-2-methyl-1,3-propanediol, jetanolamine, 4-phenolsulfonic acid, 2-aminoethylsulfonic acid, alanine,
Boric acid, tetraethylenediamine, ethanolamine,
and their salts. Two or more of these compounds may be used in combination.

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

The amount of the buffering agent of the present invention to be added is preferably 0.01 mol/Q to 0.5 mol/Q, particularly preferably 0.05 to 0.03 mol/Q, in order to keep the pH stable.

The processing liquid having a fixing ability according to the present invention may contain a buffer other than the above-mentioned buffer of the present invention.

It is desirable that the processing agent having fixing ability according to the present invention further contains a large amount of a rehalogenating agent such as an alkali halide or an ammonium halide, such as potassium bromide, sodium bromide, sodium chloride, or ammonium bromide. . Also, borates, oxalates, acetates, carbonates, phosphoric acid salts, etc.
8. Buffers, alkylamines, polyethylene oxides, and other substances known to be added to normal fixing solutions and bleach-fixing solutions can be added as appropriate.

The fixing agent is used in an amount of 0.1 mol or more per 1Q of processing liquid, preferably 0.6 mol to 0.6 mol in terms of the desired effect 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.

When the processing solution having fixing ability according to the present invention is a bleach-fix solution, the bleaching agent used in the bleach-fix solution is preferably a ferric complex salt of an aminocarboxylic acid or an aminosulfonic acid. The aminocarboxylic acid and aminosulfonic acid represent an amino compound having at least two or more carboxylic acid groups and an amino compound having at least two or more phosphonic acid groups, respectively, and are preferably represented by the following formulas (IV) and ( V).

General formula (IV) General formula (V) In general formulas (mV) and (V), E represents a substituted or unsubstituted alkylene group, cycloalkylene group, phenylene group, -RsORsORsORi- or -RsZRs-, and Z represents )NR, -A, , )NA, represents R,
~R, each represents a substituted or unsubstituted alkylene group, and A
1 to A are each a hydrogen atom, -OH, -COOM or -
PO3(M)! , M represents a hydrogen atom or an alkali metal atom.

Next, preferred specific examples of the compounds represented by these formulas [■] and (V) are listed below.

[Exemplary compound] (IV-1) Ethylenediaminetetraacetic acid (IV-2)
Diethylenetriaminepentaacetic acid (IV-3) Ethylenediamine-N-(β-hydroxyethyl-, N, N'
, N'-Triacetic acid (1!/-4) 1.3-Propylenediaminetetraacetic acid (IV-5) Triethylenetetraminehexaacetic acid (IV-6') Cyclohexanediaminetetraacetic acid (rV-7) 1.2- Diaminopropane tetraacetic acid (IV-8) 1,3-diaminopropan-2-ol tetraacetic acid (EV-9) Ethyl ether diamine tetraacetic acid (■-
10) Glycol ether diamine tetraacetic acid (TV-11) Ethylene diamine tetrapropionic acid (■-12) Phenyl diamine tetraacetic acid (■-13)
) Ethylenediaminetetraacetic acid disodium salt (rv-14) Ethylenediaminetetraacetic acid tetra(
trimethylammonium) salt (■-15) Ethylenediaminetetraacetic acid tetrasodium salt (IV-16) Diethylenetriaminepentaacetic acid pentasodium salt (IV-17) Ethylenediamine-N-(β-hydroxyethyl)-N, N', -N' -Triacetic acid sodium salt (IV-18) Propylenediaminetetraacetic acid sodium salt (IV-19) Ethylenediaminetetramethylenephosphonic acid (RV-20) Cyclohexanediaminetetraacetic acid sodium salt (■-21) Diethylenetriaminepentamethylenephosphonic acid (IV- 22) Cyclohexanediaminetetramethylenephosphonic acid (V-1) Nitrilotriacetic acid (V-2) Methyliminodiacetic acid (V-3) Hydroxyethyliminodiacetic acid (V-4) Nitrilotripropionic acid (V-5) Nitrilotrimethylenephosphonic acid ( V-6)
Iminodimethylenephosphonic acid (V-7) Hydroxyethyliminodimethylenephosphonic acid (V-8) Nitrilotriacetic acid trisodium salt Among these aminocarboxylic acids and aminophosphonic acids, it is particularly preferably used from the viewpoint of the desired effect of the present invention. Examples of compounds include (rV-1), (IV-2), (IV-4)
, (II/-6), (IV-7), (IV-10
), (mV-19), (V-1), and (V-5).

Among these, (!V-4) is particularly preferred from the viewpoint of the desired effects of the present invention.

The ferric complex salt of the organic acid is used as a free acid (hydrogen salt), an alkali metal salt such as a sodium salt, potassium salt, or lithium salt, or an ammonium salt, or a water-soluble amine salt such as a triethanolamine salt. However, preferably the potassium, sodium and ammonium salts are used. At least one type of these ferric complex salts may be used, but two or more types can also be used in combination. The amount used can be arbitrarily selected and needs to be selected depending on the silver amount and silver halide composition of the photosensitive material to be processed, but for example, it can be used in an amount of 0.01 mol or more per bleach-fix solution IQ, and is preferably It is used in an amount of 0.05 to 1.0 mol. still,
In the replenisher, it is desirable to use it in a highly concentrated form with the highest solubility in order to achieve high concentration and low replenishment.

In the present invention, in order to increase the activity of the bleach or bleach-fix solution, air or oxygen may be blown into the processing bath and the processing replenisher storage tank, if desired, or a suitable oxidizing agent, e.g. hydrogen peroxide, bromate,
Persulfates and the like may be added as appropriate.

When carrying out the method of the present invention, silver may be recovered from the fixer or bleach-fixer by known methods.

For example, the electrolysis method (described in French Patent No. 2,299.667), the precipitation method (described in JP-A-52-73037, Narrow Patent No. 2,331-220), the ion-exchange method (described in JP-A-52-73037),
1-17114, German Patent No. 2,548.237), metal substitution method (as described in British Patent No. 1,353.805), etc. can be effectively used.

It is particularly preferable to recover silver from the tank solution in-line, since the rapid processability becomes even better, but silver may also be recovered from the overflow waste solution and reused.

The fixing solution and the bleach-fixing solution according to the present invention produce remarkable effects when the replenishment amount is 20 to 65011+2, particularly 30 to 400a+Q, per 1 m'' of light-sensitive material.

In addition, iodides (ammonium iodide, potassium iodide, sodium iodide,
When containing 0.1 to 10 g/+2 of lithium iodide, etc.) and/or thiocyanate (for example, sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, etc.), the effects of the present invention are further enhanced. Especially from 0.3
5g #l, especially 0.5-3g #2. Most preferably good results are obtained between 0.8 and 2 g IQ.

The fixers and bleach-fixers of the present invention can contain sulfites and sulfite-releasing compounds, such as potassium sulfite, sodium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite. , potassium metabisulfite,
Examples include sodium metabisulfite and ammonium metabisulfite. Furthermore, the following general formula CB-1) or CB-2
) are also included.

General formula (B-1) ta General formula (B-2) In the formula, R1 is a hydrogen atom or a C1-5 alkyl group, Ro is an optionally substituted C1-5 alkyl group,
M is an alkali metal atom, R3 and R2 are each a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms, n
represents an integer from 0 to 4.

Preferred specific examples of the compounds represented by formulas (B-1) and (B-23) are shown below.

B-1 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 Sodium Bisulfite B- 7β-Methylglutaraldehyde Sodium Bisulfite B-8 Maleic Dialdehyde Sodium Bisbisulfite These sulfites and sulfite-releasing compounds often contain at least 81 moles of sulfite per lI2 of fixer or bleach-fixer. , 0.12 mol/a to 0.65 mol/a
A range of Q is preferred, and a range of 0.15 mol/a to 0.50 mol/I2 is particularly preferred. especially 0.20
A range of mol/Q to 0.40 mol IQ is preferred. However, the number of moles of these sulfites and sulfite-releasing compounds are shown in values converted to sulfite.

The processing time of the processing liquid having fixing ability is preferably 3 minutes 10 seconds or less, particularly preferably 10 seconds to 2 minutes 40 seconds, particularly preferably 20 minutes or less, from the viewpoint of the desired effect of the present invention. It ranges from seconds to 2 minutes lO seconds.

In the processing method of the present invention, it is preferable that the bleaching solution, the fixing solution, and the bleach-fixing solution be forcibly stirred. The reason for this is not only to better achieve the desired effects of the present invention, but also from the viewpoint of suitability for rapid processing.

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

Preferred specific treatment method steps of the treatment method according to the present invention are shown below. However, the present invention is not limited to these steps. - Bleach constant - 1st stability - 2nd stability (5
) Color development → bleaching → bleach-fixing → washing (6) color development → bleaching → bleach-fixing → washing → stabilization (7) color development → bleaching - bleach-fixing - stable (8) color development → bleaching → bleach-fixing → first stage Stable → second stable (or subsequently third stable) Among these steps, especially (3), (4), (7),
(8) is preferred, particularly (3) and (4).

The color developing solution according to the present invention includes alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide,
ammonium hydroxide, sodium carbonate, potassium carbonate,
It may contain sodium sulfate, sodium metaborate, borax, etc., and various additives such as benzyl alcohol, alkali metal silver halides, such as potassium bromide or potassium chloride, or development regulators such as citradinic acid, etc. Hydroxylamine or sulfite or the like may be contained as a preservative.

Furthermore, various antifoaming agents and surfactants, methanol,
An organic solvent such as dimethylformamide or dimethylsulfoxide may be appropriately contained.

Further, the p8 of the developer according to the present invention is usually 7 or more, and more preferably about 9 to 13.

In addition, the color developer used in the present invention may contain hydroxylamine, tetronic acid,
Tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid,
Pentose or hexose, pyrogallol-1,3-
Dimethyl ether and the like may also be contained.

Moreover, various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution according to the present invention. For example, as the chelating agent, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, l
-organic phosphonic acids such as hydroxyethylidene-1,1-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphonic acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1, Examples include phosphonocarboxylic acids such as 2,4-)licarponic 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.
Preferably, it is 5X 10-” mole/12 or more,
More preferably 2. OX 10-'' mole/Q or more.

In the present invention, the effect of the object of the present invention is particularly improved when the fixer or bleach-fixer is followed by a stabilizing solution.

When the method of the present invention includes processing with a stabilizing solution, the amount of stabilizing solution to be replenished is 1 to 80 times the amount brought in from the prebath per unit area of color photographic light-sensitive material to be processed, particularly 2 to 80 times.
The concentration of the pre-bath component (bleach-fix solution or fixer) in the stabilizing solution is preferably 11,500 or less in the final stabilizing solution tank, particularly preferably 1/1000 or less. be.

Furthermore, from the viewpoint of low pollution and liquid storage stability, the
1ooooo is preferable, more preferably l/2000
-1,150,000, the processing tank of the stabilization tank is configured.

The stabilization treatment tank is preferably composed of a plurality of tanks, and the number of the plurality of tanks is preferably 2 or more and 6 or less.

In the case where the stabilization treatment tank has 2 or more layers and 6 layers or less, it is preferable to use a countercurrent method (supply to the rear bath and overflow from the front bath) from the viewpoint of the effects of the present invention, especially from the viewpoint of low pollution. .

Particularly preferably 2 to 3 tanks, more preferably 2 tanks.

The amount of processing liquid brought in from the pre-bath varies depending on the type of photosensitive material, the conveyance speed of the automatic processor, the conveyance method, the method of squeezing the surface of the photosensitive material, etc. In this case, the carry-on amount is 50 to 150 m (2/m"), and the replenishment amount where the effect of the present invention on this carry-on amount is more remarkable is 50 ts.
Q/m" to 4.OQ/a"0) Range st;+, the replenishment amount with particularly remarkable effects is in the range of 200 to 1500+ia/m".

The treatment temperature for the treatment with the stabilizing solution is preferably in the range of 15 to 60°C, preferably 20 to 45°C.

The stabilizing liquid may contain various chelating agents.

Details of the chelating agent are described on pages 73 to 82 of the specification of the earlier patent application filed by the applicant.

In addition to the effects of the present invention, 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, for the purpose of improving image storage stability. Particularly preferred is a pH range of 5.0 to 8.5.

As the pH adjusting agent that can be contained in the stabilizing liquid, any commonly known alkaline agents or acid agents can be used.

Stabilizing liquids include organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphates, borates, hydrochloric acid, sulfates, etc.), surfactants, and preservatives. , B i
s M g s Z n SN i s A 1 s
Metal salts such as S ns T t s Z r and the like can be added. The amount of these compounds to be added is necessary to maintain the pH of the stabilizing bath according to the present invention, and in any combination that does not adversely affect the stability of color photographic images during storage and the occurrence of precipitation. I don't mind.

Anti-spill agents preferably used in the stabilizer include hydroxybenzoic acid ester compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds,
Carbamate-based compounds, morpholine-based compounds, quaternary phosphonium-based compounds, ammonium-based compounds, urea-based compounds, inxazole-based compounds, propanolamine-based compounds, sulfamide-based compounds, amino-based compounds, active halogen-releasing compounds, and benzotriazole-based compounds It is.

Details of these anti-spill agents are described on pages 84 to 90 of the specification of the earlier patent application filed by the applicant.

It is preferable to use water that has been previously deionized for use in the stabilizing solution, since this improves the anti-piping properties of the stabilizing solution, the stability of the stabilizing solution, and the image storage stability.

As a means of deionization treatment, the dielectric constant of the washing water after treatment is set to 5011 s/cm or less, or Ca and Mg ions are set to 5p.
Any material may be used as long as it reduces the temperature to pm or less, but
For example, it is preferable to use an ion exchange resin or a reverse osmosis membrane alone or in combination. Ion exchange resins and reverse osmosis membranes are described in detail in Kokai Technical Report No. 87-1984, but it is preferable to use strongly acidic H-type cation exchange resins and strongly basic OH-type anion exchange resins.

In the present invention, the salt concentration in the stabilizing solution is 11,000 pp or less, preferably 800 pp or less, which enhances the water washing effect and is good for damming of white backgrounds and anti-piling properties.

In order to achieve the effects of the present invention, 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.

Although the halogen composition in the photosensitive material to which the photosensitive material processing method of the present invention is applied is not limited, it is preferable that the average silver iodide content of all silver halide emulsions is 0.1 to 15 mol%. , more preferably 0.5 to 12 mol %, particularly preferably 3 to 10 mol %.

In the method for processing a light-sensitive material of the present invention, the average grain size of all silver halide emulsions in the light-sensitive material is not limited;
The brittleness is preferably 0 μm or less, more preferably 0.1 μm to 1.0 μm, particularly preferably 0.2 μm to 0.6 μm.
It is μm.

In the method for processing a photosensitive material of the present invention, the lower limit of the total dry film thickness of all hydrophilic colloid layers of the photosensitive material (hereinafter referred to as the film thickness on the emulsion side) is the silver halide emulsion, coupler, oil agent, and additives contained in the photosensitive material. There is a limit due to such factors, and the preferred film thickness on the emulsion side is 10 to 50 μ-, more preferably 15 to 50 μ-
It is 60 μm.

Further, the distance from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support is preferably 14 μm or more, and the distance from the emulsion layer to the lower end of the emulsion layer that is the next closest to the support is 2 μm.
It is preferably 0μ or more.

The photosensitive material according to the present invention uses an internal development method (US Pat. No. 2,376.679) in which a coupler is contained in the photosensitive material.
No. 2,801.1n), and any couplers generally known in the art can be used. For example, cyan couplers include those based on a naphthol or phenol structure and form indoaniline dyes by coupling, and magenta couplers include those having a skeletal structure of a 5-pyrazolone ring with an active methylene group and pyrazoloazole-based couplers. For example, as yellow couplers, those having a benzoylacetanilide, bivalylacetanilide, or acylacedoanilide structure having an active methylene ring, with or without a substituent at the coupling position, can be used. can.

In this way, as the coupler, both the so-called 2-equivalent type coupler and the 4-equivalent type coupler can be applied.

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

As a cyan coupler, the following formula (C-A), (C-
B) and CC-C).

? −? or may be bonded to each other to form a 5- to 6-membered heterocycle. ), z represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent.

- Formula (C-C) 0■ In the formula, R1 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and Y is a group represented by (However, R8 is an alkyl group) , represents an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and R1 represents a hydrogen atom or a group represented by R2. R3 and R8 are the same or different, and R1 is -CONR, R
I-NHCORa, NHCOORs, -NHSOJ-
NHCONR4N or -NH5OJRJs -Rs is a monovalent group, R1 is a substituent, X is a hydrogen atom or a group that leaves by reaction with an oxidized aromatic primary amine developing agent, Q is O or 11m is The integers R4 and R each represent a hydrogen atom, an aromatic group, an aliphatic group, or a heterocyclic group, R6 represents an aromatic group, an aliphatic group, or a heterocyclic group, and when m is 2 or 3, each R1 is They may be the same or different, and may be bonded to each other to form a ring, or R4 and R, R1 and R, and R1 and X may be bonded to each other to form a ring. However, when Q is O, m is 0, R is -CONHR, and R2 represents an aromatic group.

First, the above-mentioned formula (C-A) and formula (C-B) will be explained. In this formula, Y is a group represented by. Here, R1 and R1 are each an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (e.g., methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms. group (allyl group, peptadecenyl group, etc.), cycloalkyl group, preferably 5
-7-membered rings (e.g. cyclohexyl, etc.), aryl groups (e.g. phenyl, tolyl, naphthyl, etc.), heterocyclic groups, preferably 5-membered containing 1 to 4 nitrogen atoms, oxygen atoms or sulfur atoms - Represents a 6-membered ring group (eg, furyl group, thienyl group, benzothiazolyl group, etc.).

R3 represents a hydrogen atom or a group represented by R2.

R2 and R1 may be combined with each other to form a 5- to 6-membered heterocycle. Note that any substituent can be introduced into R and R2, such as an alkyl group having 1 to 10 carbon atoms (for example, methyl, i-propyl, i-butyl, t-butyl, t-octyl, etc.), Aryl groups (e.g. phenyl,
(naphthyl, etc.), halogen ionic molecules (7 atoms, chlorine, bromine, etc.)
, cyano, nitro, sulfonamide groups (e.g. methanesulfonamide, butanesulfonamide, p-toluenesulfonamide sulfamoyl group (methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl groups (e.g. methanesulfonyl, p-toluene) sulfonyl, etc.), fluorosulfonyl group, carbamoyl group (e.g. dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl group (e.g. ethoxycarbonyl, phenoxycarbonyl, etc.), acyl group (e.g. acetyl, benzoyl, etc.)
, heterocyclic groups (e.g. pyridyl group, pyrazolyl group, etc.),
Examples include an alkoxy group, an aryloxy group, an acyloxy group, and the like.

In the general formula (C-A) and -Formula 1: c-B), R
1 represents a ballast group necessary for imparting diffusion resistance to the cyan coupler represented by the general formula (C-A) and the numerical formula (C-B) and the cyan dye formed from the cyan coupler. Preferred are alkyl groups, aryl groups, alkenyl groups, cycloalkyl groups, or heterocyclic groups having 4 to 30 carbon atoms. For example, a straight-chain or branched alkyl group (e.g. t-
butyl, n-octyl, t-octyl, n.dodecyl, etc.), 5-membered or 6-membered heterocyclic groups, and the like.

- In the formula (C-A) and - formula (C-B), Z represents a hydrogen atom or a group that can be separated during the coupling reaction with the oxidized product of the N-hydroxyalkyl-substituted p-phenylenediamine derivative color developing agent. .

For example, halogen atoms (e.g. chlorine, bromine, fluorine, etc.)
, substituted or unsubstituted alkoxy group, aryloxy group,
Examples include heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, sulfonyloxy groups, alkylthio groups, arylthio groups, peterocyclic thio groups, sulfonamide groups, and more specific examples include U.S. Patent No. 3,741.5
No. 63, JP-A No. 47-37425, JP-A No. 48-36
No. 894, JP-A-50-10135, JP-A No. 50-117
No. 422, No. 50-130441, No. 51-1088
No. 41, No. 50-120343, No. 52-18315
No. 53-105226, No. 54-14736, No. 54-48237, No. 55-32071, No. 5
No. 5-65957, No. 56-1938, No. 56-12
No. 643, No. 56-27147, No. 59-14605
Examples include those described in No. 0, No. 59-166956, No. 60-24547, No. 60-35731, No. 60-37557, and the like.

In the present invention, a cyan coupler represented by the general formula (CD) is preferred.

General formula (CD) In formula (CD), R4 is a substituted or unsubstituted aryl group (particularly preferably a phenyl group). When the aryl group has a substituent, the substituent is -So
, R halogen atom (fluorine, chlorine bromine, etc.), -CF,
, -No2, -CN, -CORii-cooR,, -so
,oR.

At least one substituent selected from is included.

Here, R is an alkyl group, preferably having 1 to 20 carbon atoms.
alkyl groups (e.g. methyl, ethyl, 1-butyl,
dodecyl groups, etc.), alkenyl groups preferably having 2 carbon atoms
~20 alkenyl groups (allyl group, veptadecenyl group, etc.), cycloalkyl groups, preferably those with 5- to 7-membered rings (
For example, cyclohexyl, etc.), aryl group (for example, phenyl group, tolyl group, naphthyl group, etc.), and R is a hydrogen atom or a group represented by R6.

In the compound represented by the general formula (CD) suitable as the cyan coupler of the present invention, R1 is a substituted or unsubstituted phenyl group, and the substituent to the phenyl group is cyano, nitro, -5OJy (Rr is alkyl group) halogen atom,
A compound that is trifluoromethyl.

In the general formula (C-D), 2 and R are each - formula (C
-A) and (C-B) have the same meaning. R3
Preferred examples of the ballast group represented by the following formula (C
-E).

- Formula (C-E) In the formula, J represents an oxygen atom, a sulfur atom, or a sulfonyl group, k represents an integer from O to 4, Q represents 0 or l, and when k is 2 or more, 2 or more R that exists.

may be the same or different, and R8 has 1 to 2 carbon atoms.
%RI represents a monovalent group, preferably a hydrogen atom, a halogen atom (e.g. chlorine, bromine), an alkyl group, preferably a linear or branched alkylene group, and a substituted alkylene group such as an aryl group. Branched alkyl groups having 1 to 20 carbon atoms (e.g. 6 groups such as methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.), aryl groups (e.g. phenyl group), heterocyclic groups (for example, a nitrogen-containing heterocyclic group), an alkoxy group, preferably a linear or branched alkoxy group having 1 to 20 carbon atoms (for example, 6 groups such as methoxy, ethoxy, t-butyloxy, octyloxy, decyloxy, dodecyloxy, etc.)
, aryloxy group (e.g. phenoxy group), hydroxy group, acyloxy group, preferably alkylcarbonyloxy group, arylcarbonyloxy group (e.g. acetoxy group, benzoyloxy group), carboxy, alkyloxycarbonyl group, preferably carbon number 1- 20 straight chain or branched alkylcarbonyl group, preferably phenoxycarbonyl group, alkylthio group, preferably acyl group having 1 to 20 carbon atoms, preferably straight chain or branched alkylcarbonyl group having 1 to 20 carbon atoms, acylamino group , preferably a straight chain or branched alkylcarboxamide group having 1 to 20 carbon atoms, a benzenecarboxamide group, a sulfonamide group, preferably a straight chain or branched alkylsulfonamide group having 1 to 20 carbon atoms or a benzenesulfonamide group, Carbamoyl group, preferably a linear or branched alkylaminocarbonyl group having 1 to 20 carbon atoms or phenylaminocarbonyl group, sulfamoyl group, preferably e.g. 1 to 2
0 linear or branched alkylaminosulfonyl group or phenylaminosulfonyl group.

Next, specific examples of compounds of the cyankabu 2- of the present invention represented by the general formula (C-A) or (C-B) are shown on pages 105 to 119 of the specification of the earlier patent application filed by the applicant. Examples include those listed on the page.

Next, general formula (CC) will be explained.

- The six groups represented by R3-R2 in formula (C-C) include those having substituents.

R6 is an aliphatic group having 1 to 30 carbon atoms, and 6 to 3 carbon atoms.
An aromatic group having 0 carbon atoms and a heterocyclic group having 1 to 30 carbon atoms are preferable, and those mentioned as preferable examples for R and R are preferably hydrogen atoms and R4.

R2 is direct or -NH-, -CO- or -S
Hydrogen atom bonded to -NH- via O, -, carbon number 1
~30 aliphatic groups, C6-30 aromatic groups, C1-30 heterocyclic groups, -0R-COR@, PO(O
R111)! , -Po(R+o)z, COJ+o
, -So! R.

Or・So,OR,. (R, , R1 and R11l are the same as defined for R1 and R6 above, respectively, and Ra and R9 may be combined to form a petero ring.) is preferred.

R2 is preferably an aromatic group having 6 to 30 carbon atoms,
Representative examples of substituents for R7 include a rhodane 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, and a carno(moyl group). , sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group,
Examples include an aliphatic sulfonyl group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group, an imide group, an aliphatic group, and an aliphatic oxycarbonyl group.

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

Typical examples of R3 include halogen atom, hydroxy group, amino group, carboxyl group, sulfonic acid group, cyano group, aromatic group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, Examples include 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, etc. and this R1
The number of carbon atoms contained in is preferably θ to 30. An example of cyclic R3 when m=2 is a dioxymethylene group.

When a is 1, RX is particularly preferably -CONR,R, m is preferably O, and R3 is directly bonded to -NH- -COOR+o, -SO*R+o, -CO
NRsRs, -5O*NRsR* is particularly preferred, and even more preferred is -〇〇R, which directly binds to NH.
. ,-COR iichi 5o! RIO, especially -COO
Rto is most preferred.

Also included in the present invention are those that form a 2l or more multimer through R1 to R,,X.

- Among formulas (C-C), the case of 12-0 is preferable.

Specific examples of couplers represented by the general formula (C-C) are JP-A-60-237448, JP-A No. 61-153640, JP-A No. 6
No. 1-145557, No. 62-85242, No. 48-
No. 15529, No. 50-117422, No. 52-18
No. 315, No. 52-90932, No. 53-52423
No. 54-48237, No. 54-66129, No. 55-32071, No. 55.65957, No. 55-
No. 105226, No. 56-1938, No. 56.126
No. 43, No. 56-27147, No. 56-126832
No. 58-95346 and U.S. Patent No. 3,488.1
No. 93, etc., and can be synthesized by the methods described therein.

Depending on the physical properties (e.g. solubility) of the coupler, the coupler can be added to the photosensitive material using an oil-in-water emulsion dispersion method using a water-insoluble high-boiling organic solvent, an alkaline dispersion method adding it as an alkaline solution, or a latex dispersion method. Various methods can be used, such as a solid dispersion method in which the compound is directly added as a fine solid.

The amount of coupler added is usually 1.2 mm per mole of silver halide. O
X 10-” to 1.0 mol, preferably 5.OX 10
-'' to 8, OX 10-' moles.

Next, typical specific examples of the coupler represented by the general formula (CC) are those described on pages 124 to 142 of the specification of the earlier patent application filed by the applicant.

The amount of the cyan coupler preferably used in the present invention is usually in the range of 1X10-'' to 1 mole, preferably 5X10-'' to 8X10-mol per mole of silver halide.

At least one of the photographic constituent layers constituting the photosensitive material of the present invention
At least one of the layers, especially the green-sensitive emulsion layer, has the following formula - (
It is preferable to contain a magenta cobra represented by M-1) in order to highly effectively achieve the object of the present invention.

6.

-Formula CM-1) V In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by 2 may have a substituent. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

In formula (M-1) above, the substituent represented by R is not particularly limited, but typically includes 6 such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc. Other groups include halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, 6 groups: amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, spiro compound residues, bridged hydrocarbon compound residues etc. can also be mentioned.

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

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

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.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

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

The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc.; Acyl E includes alkylcarbonyl group, arylcarbonyl group, etc.; carbamoyl group includes alkylcarbamoyl group, arylcarbamoyl group, etc.; sulfamoyl group includes alkylsulfamoyl group,
Arylsulfamoyl group; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc.; As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc.; As an ureido group, an alkylureido group, an arylureido group, etc.: Examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group; as the heterocyclic group, a 5- to 7-membered group is preferable, specifically a 2-furyl group, a 2-thienyl group, a 2-thienyl group, and a 2-membered heterocyclic group. -Pyrimidinyl group, 2-benzothiazolyl group, etc.: The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, such as 3.
4.5-tetrahydropyranyl-2-oxy group, l-
Phenyltetrazole, 5-oxy group, etc.; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2.4-diphenoxy-1, 3,5-triazole-6 monothio group, etc.; Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-heptadecylsuccinimide group, phthalimide group , glutarimide group, etc.; as a spiro compound residue, spO[3,3]hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2°2.1
1 hebutan-1-yl, tricyclo [3,3,1,1
”]]decane-1-4-7.7-dimethyl-bisic I:
l[2,2,l]hebutan-1-yl and the like.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxycarbonylthio, acylamino, sulfonamide, N[nitrogen-containing heterocycle bonded with child, alkyloxycarbonylamino , aryloxycarbonylamino, carboxyl, (R1' is the same as the above R, Z' is the same as the above 2, and R8', R, and I represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group) ) and the like, preferably a halogen atom, particularly a chlorine atom.

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

More specifically, what is represented by the general formula CM-1) is represented by, for example, the following formula (M-n) to general formula M-■.

General formula CM-11) General formula [M-In) Moeki general formula CM-I? ) ~ general formula M-■], R
3 to R and X have the same meanings as R above.

Also, among the formulas CM-1), preferred are those represented by the following formula [M-■].

- Formula CM-IV) General formula (M-V) General formula CM-Vl) General formula [M-■] In the formula, R, , X and Zt are R in the general formula CM-I),
It is synonymous with X and Z.

Among the magenta couplers represented by formula (M-11) to general formula M-■, particularly preferred are those represented by general formula CM
It is a magenta coupler represented by -11).

The ring formed by 2 in general formula (M-1) and -
The substituent that the ring formed by 2 in formula [M-■] may have, and R3-R8 in formula CM-1) to general formula M-Vl) are the following formula C
Those represented by M-II) are preferred.

-Formula CM -ff) -R'-So! -R' In the formula, R1 represents an alkylene group, and R2 represents an alkyl group, a cycloalkyl group, or an aryl group.

The alkylene group represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and it does not matter whether the straight chain has one branch or not.

The alkyl group represented by R2 is preferably a 5- to 6-membered one.

In addition, when used for positive image formation, the substituent R on the heterocycle
And R1 is most preferably represented by the following formula (M-X
).

-Math CM-X) R9 Electron Rlo -C- "In the formula, R,, R10 and R11 each have the same meaning as R above.

Also, two of the above R1° and R11, for example, R9
and R3゜ may be combined to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and furthermore, Ro may be combined with the ring to form an endowed hydrocarbon compound residue. It's okay.

-Formula CM-X) is preferably (t)Rs~
A small number of R0 (if both are alkyl groups, (i)
At least one of R1 to R11, for example R1, is a hydrogen atom, and the other two R.

and R4° combine to form a cycloalkyl together with the root carbon atom.

Furthermore, it is preferable among (i) that two of R9 to R11 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

In addition, when used for negative image formation, the substituent R on the heterocycle
and R, most preferably the following formula CM-
II).

-Formula (M-n) R1m -CH*- R1 in the ceremony! has the same meaning as R above.

R1! Preferred is a hydrogen atom or an alkyl group.

Typical specific examples of magenta couplers preferably used in the present invention include compounds 1 to 77 described on pages 48 to 64 of Japanese Patent Application No. 180310/1982, as well as 61-9791 specification, pages 66-1
Among the compounds described on page 22, Nos. 1 to 4.
6.8-17.19-24.26-43.45-59.
61-104, 106-121.123-162.16
Compounds represented by 4 to 223 can be mentioned. In addition, the magenta coupler is used in the Journal of the Chemical Society 4.
chemical 5ociety).

Perkin I (1977), 204
7-2052, U.S. Pat.
No. 162548, No. 59-171956, No. 60-3
No. 3552, No. 60-43659, No. 60-1729
It can be synthesized by referring to No. 82 and No. 60-190779.

The magenta coupler is usually 1 mole of silver halide.
Xl0-3 to 1 mol, preferably lXl0-'' to 8X
A range of 10-' moles can be used.

The magenta dye-forming coupler preferably used in the present invention can be represented by the following formula CM-1].

Ar Ar: A phenyl group, especially a substituted phenyl group.

Examples of the substituent include 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 sulfonamido group, and an acylamino group.
The phenyl group represented by may have two or more substituents.

Specific examples of substituents are listed below.

Halogen atom: chlorine, bromine, fluorine Alkyl group: Methyl group, ethyl group, 1so-propyl group, butyl group, t-butyl group, L-pentyl group, etc., but alkyl groups having 1 to 5 carbon atoms are particularly preferred .

Alfoxy group: methoxy group, ethoxy group, butoxy group,
Examples include 5ea-butoxy group, 1so-pentyloxy group, and particularly preferred is an alkoxy group having 1 to 5 carbon atoms.

Aryloxy group: phenoxy group, β-naphthoxy group, etc., but this aryl moiety may further have the same substituents as those listed for the phenyl group represented by A.

Alfkidicarbonyl group: A carbonyl group with an alkoxy group as described above, and the number of carbon atoms in the alkyl part of methoxycarbonyl group, pentyloxycarbonyl group, etc. is 1 to 5
Preferably.

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

Sulfamoyl group: sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group
Alkylsulfamoyl groups such as moyl groups.

Sulfonyl group: Alkylsulfonyl group such as methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, and arylsulfonyl group.

Sulfonamide group: an alkylsulfonamide group such as a methanesulfonamide group or a toluenesulfonamide group, or an arylsulfonamide group.

Acylamino group: acetamino group, pivaloylamino group, benzamide group, etc.

Particularly preferred are halogen atoms, and among these, chlorine is most preferred.

Yap - Represents a group that leaves when a dye is formed by coupling with an oxidized product of a diamine color developing agent.

Specifically, for example, it is necessary to form a 5- to 6-membered ring with a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an aryl group, and an atom selected from among carbon atoms, ugly atoms, nitrogen atoms, and sulfur atoms. Represents a group of atoms. ) Specific examples are given below.

Halogen atoms: chlorine, bromine, fluorine.

Alkoxy group: ethoxy group, benzyloxy group, methoxyethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group, etc.

Aryloxy group: phenoxy group, 4-methoxyphenoxy group, 4-nitrophenoxy group, etc.

Acyloxy group: acetoxy group, myristoyloxy group, benzoyloxy group, etc. Arylthio group: phenylthio group, 2-butoxy, 5,
octylphenylthio group, 2.5-dihexyloxyphenylthio group, etc.

Alkylthio groups: methylthio group, octylthio group, hexadecylthio group, benzylthio group, 2-(diethylamino)ethylthio group, ethoxycarbonylmethylthio group, phenoxyethylthio group, etc.

Acyl group, tetrazolyl group, etc. R: When R is an acylamino group, examples thereof include acetamido group, isobutylamino group, benzamide group, 3-[
α-(2,4-di-tert-amylphenoxy)butyramide 1 benzamide group, 3-Ca-(2,4-di-tert-amylphenoxy)
tart・amylphenoxy)acetamide]benzamide group, 3-[g(3-pentadecylphenoxy)butyramide 1benzamide group, a-(2,4-di・ter
R When is an anilino group, examples thereof include anilino group, 2-chloroanilino group, 2,4-dichloroanilino group, 2.5-dichloroanilino group, 2.
4-dichloroanilino group, 2.5-dichloroanilino group, 2.4.5-trichloroanilino group, 2-chloro-5
-(3-octadecenylsuccinimide)anilino group,
2-chloro-5.[a-(3-tart-butyl-4-
hydroxy)tetradecanamido)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, etc., and R
When is a ureido group, examples include 3.((2,4-di-tert-aminophenoxy)acetamido)phenylureido group, phenylureido group, methylureido group, octadecylureido group, 3-tetradecanamide phenylureido group, or There are N,N-dioctylureido groups and the like.

Among the compounds represented by the general formula CM-u), particularly preferred compounds are represented by the general formula (M-n).

-Math CM -IN) ■ Ar In the formula, Y and Ar represent the same meanings as in general formula (M-11).

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

Specific examples are listed below.

Halogen atoms: chlorine, bromine, fluorine alkoxy groups: methoxy group, ethoxy group, butoxy group,
Alkoxy groups having 1 to 5 carbon atoms such as 5ec-butoxy group and i-pentyloxy group are preferred.

Alkyl group: methyl group, ethyl group, s 1so-propyl group, butyl group, t-butyl group, t-pentyl group, etc.

is preferably an alkyl group having 1 to 5 carbon atoms.

Particularly preferred is a halogen atom, with chlorine being particularly preferred.

R1: represents a group that can be substituted on the benzene ring, n is l or 2
represents. When n is 2, R1 may be the same or different.

Examples of groups that can be substituted on the benzene ring represented by R+ include a halogen atom, R'-1R'〇-R', R'' and R''' may be the same or different, and a hydrogen atom or a substituent, respectively. represents an alkyl group, alkenyl group or aryl group which may have Among these, specific examples of magenta couplers preferably used in the present invention are those described on pages 42 to 51 of Japanese Patent Application No. 131590/1982 and Japanese Patent Application No. 172154/1983.
These couplers are disclosed in JP-A No. 56-38043.
No. 57-14837, No. 57-204036,
It can be easily synthesized according to the method described in No. 58/14833.

The amount of these magenta couplers added is preferably Q,005 to 2 moles per mole of silver halide, more preferably 0.
．． 01-1 mole.

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

When the light-sensitive material of the present invention has two or more light-sensitive 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 planar silver halide emulsion, but in addition to this,
Any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloride, and silver chloride may be used. As protective colloids for these silver halides, in addition to natural products such as gelatin, various synthetically obtained colloids can be used.

The silver halide emulsion may contain conventional photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants.

As the light-sensitive material used in the present invention, color negative film, color paper, color reversal film, color reversal paper, etc. can all be used.

[Effects of the Invention] According to the present invention, there is provided a method for processing a photosensitive material, in which processing is performed immediately with a bleaching solution after color development, followed by processing with a processing solution having fixing ability, and the processing with the bleaching solution is speeded up. The present invention provides a processing method in which bleaching blade blur, poor color restoration, and deterioration in storage stability of a processing solution having a fixing ability caused by mixing of a bleaching solution into a processing solution having a fixing ability are provided.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 In all Examples, the amount added in the silver halide photographic light-sensitive material is expressed in g per 1 m2 unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver.

An ultrahigh-sensitivity multilayer color photographic material was prepared on a cellulose triacetate film support, consisting of each layer having the composition shown below.

1st layer: Halicon prevention layer Black colloidal silver ...0.2 Gelatin ...1.7 Ultraviolet absorber (U
V-1) ...0.3 colored coupler (
CM-1)...0.2 Oil for dispersing ultraviolet absorbent (oil-1)...0.15 Oil for dispersing ultraviolet absorbent (oil-2)...0.
15 Colored coupler dispersion oil (oi 1-3) -0,2 2nd layer: Intermediate layer gelatin...1.2 3rd layer;
First red-sensitive emulsion layer Silver iodobromide emulsion (Ear-1)...1.0
Silver iodobromide emulsion (Elm-2)...0.5
Gelatin...1.3 Sensitizing dye (S-1)...0.5X l□-' (mol/silver 1 mole) Sensitizing dye (S-2)...2 Xl0-'
(Mole/1 mole of silver) Sensitizing dye (S-3)...2 Xl0 mouth (mol/1 mole of silver) Cyan coupler (C'-1)...0.07
Cyan coupler (C''-2)...0.3 Cyan coupler (C'-4)...0.3 Colored cyan coupler (CG-1)...0.07 DIR compound (D-1) ...0.0
05 (c -1), (C'-2), (c -4), (c
c-1).

Dispersion oil (oil-1) of (D-1)...0
．． 2 4th layer: Intermediate layer gelatin...0.8 5th layer:
First green-sensitive emulsion layer Silver iodobromide emulsion (Ear-1)...1°O
Silver iodobromide emulsion (Es-2) ...0.5 Gelatin ...1.4 Sensitizing dye (
S-4) ...1.8X 10-' (mol/
1 mole of silver) Sensitizing dye (S-5)...1.3X 10-
'(mol/silver 1 mol) Sensitizing dye (S-6) ・9.2X 1O-s
(Mole/1 mole of silver) Sensitizing dye (S-7) ・6.8X 10-'
(Mole/1 mole of silver) Sensitizing dye (S-8)...6.2X 10-
'(Mole/1 mole of silver) Magenta coupler (M'-1)...0.15
Colored magenta coupler (CM-1)...0.08 (M'-1), (CM-1) dispersion oil (of 1)
-3) ...0.23 6th layer: Intermediate layer gelatin color stain preventive agent (SC-1) ...0.8 ...0.05 (SC-1) dispersion oil (oil-3) ) ...0
．． 05 7th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (Em-1)...0.8 Gelatin...0.6 Sensitizing dye (
S-9) ...3 Xl0-4 (mol/silver 1 mol) Sensitizing dye (S-10) ・l X 10-'
(Mole/1 mole of silver) Yellow coupler (Y'-1)...0.3(
Y''-1) dispersion oil (off-3) -0,3 8th layer: Intermediate layer gelatin...0.8 Color stain inhibitor (SC-1)...0.05 (SC-
1) Dispersion oil (oil-3)...0.05 9th
Layers: Second red-sensitive emulsion layer Silver iodobromide emulsion (Em-1)...1.0 Silver iodobromide emulsion (Es+-3)...2.0 fine grain AgX emulsion (average grain size 0.08 Psi) )Agl =
2 mol% silver iodobromide...0.5 gelatin
...2.4 1st θ layer sensitizing dye (S-1) ...0.2X 10-
'(mol/silver 1 mol) Sensitizing dye (S-2) ``-1,Ox 10-''
(Mole/1 mole of silver) Cyan coupler (C''-1)...0.2 Cyan coupler (C'-3)...0.05 Cyan coupler (C''-4)...0.10 color Anti-staining agent (SC-1)...0.05 (C'
-1), (C''-3), (C'-4), (SC-1)
Dispersion oil (oil-1)...0-
4: Intermediate layer gelatin...0.8 Color stain inhibitor (SC-1)...0.07 Colored magenta coupler (CM-1)...0.04 (SC-1), (CM-1 ) dispersion oil (oil-
3) 11th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (Em-1) Silver iodobromide emulsion (Em-3) ...0.25 ...0.8 ...1.6 12th layer: 13th layer: Gelatin...1.6 Sensitizing dye (S-4)...6.8X 10-' (mol/silver 1 mol) Sensitizing dye (S-5) ・6. 7X 10-'(
mol/1 mol of silver) Sensitizing dye (S-6) ・2.1 x 10-
'(Mole/1 mole of silver) Magenta coupler (M'-1)...0.2 Colored magenta coupler (CM-1)...0.02 Dispersion of (M'-1), (CM-1) oil (oi)
l-4) = J, 2 intermediate layer fine grain AgX emulsion (average particle size 0.08 μ-) Agl = 2
Mol% silver bromide...0.3 gelatin
...0.8 color stain prevention agent (SC-
1) ・-0.05 (SC-1) dispersion oil (oil-3) ・=0.4 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Ea-1) ...0.7 14th Layered silver iodobromide emulsion (Es-4)...1.4 fine grain AgX emulsion (average grain size 0.08 μs) Agl =
2 mol% silver iodobromide...0.1 fine grain AgX
Emulsion (average grain size 0.3 μl) Agl -2 mol% silver iodobromide ...0.1 gelatin
...2.1 Sensitizing dye (s-10) ...
・0.4X 10-' (mol/silver 1 mol) Sensitizing dye (s-11) ...1.2X 10
-' (mol/silver 1 mol) Yellow coupler (Y''-1) ...0.8 (Y
'-1) Dispersion oil (oil-3) -0,8 = First protective layer gelatin...1.5 Ultraviolet absorber (UV-1)...0.1 Ultraviolet absorber (UV-2 ) ...0.1 Formalin scavenger (HS-1) ...0.5 Formalin scavenger (HS-2) ...0.2 Oil for dispersing ultraviolet absorber (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 μm layer)...0.12 Polymethyl methacrylate (average particle size 3 μm)...0.02 Sheli Agent (IIAX-1) ・0.04 Charge control agent (Real-1) ...0,004
In addition to the above composition, each layer contains coating aid 5u-11, dispersion aid 5u-2 and 5u-3, and hardening agent 1(-1 and H-1).
2. Stabilizer St IN to antifoggant F-1 and A
Add F-2-2.

a-1 Cocoon average grain size 0.8μ, average silver iodide content 8.0%, monodisperse surface low silver iodide content emulsion m-2 Average grain size 0.40μ■, average silver iodide content 7.0%, monodisperse, low surface silver iodide content emulsion E+s-3, average grain size 1.6μ, average silver iodide content, monodisperse, surface low silver iodide content emulsion E@-4 Average grain size 2.02 m, average silver iodide content 6.4%, 7.0%, -t-6- (CH.,)sSOs'''(C*Ha)sNHS -1
0 M-1 a T-1 P-1 P-2' -1 S-1 S-2 5C-1 (COx)xsOsK Na0ss-C-C00CHaCCFnCFt)sHC
C00CH*(CFzCFz)3l Day 8 AX-1 U-1 ■ 0th -1 1l-2 o i 1-3 0low 4 0■ G*NI*(t,) The photosensitive material prepared as in 2. After wedge exposure using white light, the following development process was performed.

Experimental processing Processing process Processing time Processing temperature Color development
3 minutes 15 seconds 38℃ bleaching
45 seconds 37℃ constant
Arrive 90 seconds 37
℃ stabilization 60 seconds 37℃ drying 60 seconds
The composition of the treatment solution used at 70°C is as follows.

Color developer Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 4g Sodium bromide
1.3g potassium iodide
1.2mg hydroxylamine sulfate
2.5g sodium chloride
0.684-amino-3-methyl-N-ethyl-N-(
β-hydroxylethyl) aniline sulfate 4.8g Potassium hydroxide 1.2g Add water to 11
2 and pH 1 using potassium hydroxide or 50% sulfuric acid.
Adjust to 0.06.

Bleach liquid Bleach listed in Table 1 Add 150g of ammonium bromide water to IQ
and adjust the pH to 5.5 using aqueous ammonia or glacial acetic acid.

Ammonium thiosulfate 250 g Ammonium sulfite 20 g Imidazole (buffer of the present invention) 20 g Water was added to bring the volume to 112, and the pH was adjusted to 7.0 using acetic acid and aqueous ammonia.

Stabilizing liquid formaldehyde (37% solution) 2ml
5-Chloro-2-methyl-4-isothiazolin-3-one 0.05g emulgen ato was added with 2g of sodium formaldehyde bisulfite adduct to bring it to IQ, and the pH was adjusted to 7.0 with aqueous ammonia and 50% sulfuric acid.
Adjust to.

Optical densitometer PDA-65A for developed samples
(manufactured by Konica Corporation), the yellow, magenta, and cyan densities of the minimum density part were measured using blue light, green light, and red light, respectively, as the bleaching blade blur characteristic, and the maximum density as the cyan restoration failure characteristic. The red light density of the density area was measured. The above results are shown in Table 1. From Table 1, it can be seen that the bleaching solution containing the compound of the general formula (A) as a bleaching agent was used for 90 seconds or less, and that even a processing solution having a fixing ability that is detrimental to the present invention could be used. The method of the present invention uses only ferric salt of ethylenediaminetetraacetic acid as a bleaching agent, and the bleaching time is 99.
It can be seen that, compared to the conventional technique in which the time exceeds 0 seconds, both the bleaching blade burr and cyan restoration failure are better.

Example 2 As a fixer, the buffer was as shown in Table 2, 50 μa of bleach was added to the fixer, and the fixer was stored at 38°C for 2 weeks (the pH of Solution M was as shown in Table 2). ) was used, but the same experiment as Experiment No. 11 of Example 1 was conducted. The storage stability of the fixer was determined by visually observing the condition of the fixer after the storage. The judgment criteria are as follows.

○...No abnormality.

Δ: Slight turbidity is observed.

×...Floating substances or sediments are clearly observed.

From Table 2, in the bleaching process using the bleaching agent of the present invention within 90 seconds, the buffering agent of the present invention is used as the buffering agent of the fixing solution, and 9 tl of the fixing solution is within the scope of the present invention. This shows that it is possible to improve both bleaching edge blur, poor cyan restoration, and storage stability of the bleaching solution when the bleaching solution is mixed into the fixing solution.

Example 3 Experiment No. of Example 2 except that the treatment time with bleaching solution and the buffer and pH of the fixing solution were as shown in Table 3.

From Table 3, when the bleaching agent represented by the general formula (A) is used as the bleaching agent in the bleaching solution, the processing time with the bleaching solution is 90%.
By using the buffering agent of the present invention as a buffering agent of the fixing solution and setting the pi of the fixing solution to 6.0 to 8.5, bleaching edge blur, cyan restoration failure, and bleaching solution can be reduced. It can be seen that all three aspects of the storage stability of the bleaching solution when mixed with the fixing solution are improved.

Example 4 Example 2 except that the buffering agent of the fixer was as shown in Table 4.
An experiment similar to No. 19 was conducted. Results (Note) The amount of buffer added is 0.2 mol/12.

Table 4 shows that various buffering agents according to Yoriaki present the effects of the present invention.

Claims (1)

[Scope of Claims] In a method for processing a silver halide color photographic light-sensitive material for photographic use, which immediately processes with a bleaching solution after color development and subsequently processes with a processing solution having fixing ability, the bleaching solution has the following general formula: A buffer containing a ferric complex salt of the compound represented by [A], the processing time with a bleaching solution is 90 seconds or less, and the processing solution having fixing ability has a buffering ability at pH 6.0 to 8.5. 1. A method for processing a silver halide color photographic light-sensitive material, the method comprising: a silver halide color photographic material having a pH of 6.0 to 8.5; General formula [A] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A_1, A_2, A_3 and A_4 may be the same or different, -CH_2OH, -CO
Represents OM or -PO_3M_1M_2. M, M_1 and M_2 each represent 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. ]