JPH03260643A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To decrease the fluctuation in the sensitive and gradation of magenta by developing the photosensitive material contg. a specific magenta coupler and a prescribed silver iodobromide emulsion with a developing soln. processed by an electrophoresis method with an ion exchange membrane. CONSTITUTION:The color photographic sensitive material (A) subjected to imagewise exposing is processed with the color developing soln. (B) contg. an arom. primary amine color developing agent. The photosensitive material which contains the magenta coupler expressed by formula I and, in which >=1 layers of the layers contg. this coupler consists of the silver iodobromide emul sion contg. >=(2 to 20)mol% silver iodide is used as the photosensitive material A at this time. The developing soln. subjected to the regeneration processing with the electrophorosis method with the ion exchange membrane is used as the developing soln. B. In the formula, X denotes an elimination group; R1 denotes H or substituent; Ya to Yc denote (substd.) methyne, =N-, etc., for which the compd. of formula II, etc., are usable.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more particularly to a continuous processing method in which a color developing solution is recycled and reused using an ion exchange membrane electrodialysis method. .

(Prior Art) In a method for processing silver halide color photographic materials,
The used processing liquid is generally disposed of as an overflow liquid.

However, these used processing liquids, which are recovered and processed as waste liquids, have a large pollution load value, are not desirable for environmental conservation, and the collection and delivery costs for their recovery cannot be ignored.

In particular, regarding the color development process of color photographic light-sensitive materials, it is highly alkaline and has a high a pollution load expressed in BOD (biochemical oxygen demand), and the pollution load of waste liquid is extremely large, and the chemicals are expensive. From this point of view, various methods have been proposed to reduce waste liquid.

For example, a low replenishment processing method has been carried out in which the amount of replenishment is reduced by adjusting the color developer replenisher (hereinafter referred to as color developer replenisher) &11 composition, and Japanese Patent Application Laid-Open No. 61-251852
No. 61-26174], No. 61-282841, No. 61-70552, etc. Adjustment of the replenisher composition in low replenishment processing means, for example, concentrating consumable components such as color developing agents and preservatives in the replenisher so that the necessary amount of components can be supplied even if the replenishment amount is reduced. Measures can be cited. Furthermore, when a silver halide color photographic light-sensitive material is processed, halogen ions are released into the color developing solution, but in low replenishment processing, the bromide ion concentration in the color developing solution increases, and development is impaired. This results in suppression.

Therefore, in order to prevent this, measures are generally taken such as reducing the bromide concentration in the replenisher compared to normal replenishment processing. However, there are certain limits to this,
Accumulation of bromine ions caused delays in development, and subtle fluctuations in bromine ion concentration changed photographic properties.

On the other hand, as a means for reducing waste liquid, a method of reusing a used processing liquid (overflow liquid) as a replenisher is also being considered. If reuse becomes possible, the above-mentioned problems in waste liquid treatment will be solved, and the active ingredients remaining in the overflow liquid can also be reused, which is less expensive than creating a new replenisher. The amount of chemicals used is reduced, and further cost reductions can be achieved. Therefore, in order to be able to reuse used processing solutions, regeneration procedures generally involve redressing the fluctuations that occurred during processing, i.e. removing accumulated components that adversely affect photographic performance, and then expending them. Many studies have been conducted on so-called regeneration technology, in which the missing components are added and used again as a replenisher.

In the reproduction wave f4i, the conventional problem is how to effectively remove the accumulated components, and in the color development process, it is particularly important to remove bromine ions that are eluted from the light-sensitive material and have a strong development inhibiting effect. Na i! It was a question.

For example, a method for removing halogen using an ion exchange resin was published in S-PTE J, 8.8.168-17+ (1979
), Japanese Patent Publication No. 55144240, 53-132343
It is proposed in the No.

However, this method requires large equipment such as resin columns, requires technology to control halogen ions, and can only be processed in batches.Furthermore, a large amount of waste liquid is generated to regenerate the resin, so new methods are required for this waste liquid treatment. This poses a number of challenges.

Furthermore, a halogen removal method using ion-exchange membrane electrodialysis is described in Japanese Patent Publication No. 52459/1983 and Japanese Patent Application Laid-open No. 97432/1989, etc., and furthermore, a developer tank and an ion exchange membrane electrodialysis tank are connected, and the developing Bromine ions in the solution are detected and quantified, and based on the results, the amount of electricity supplied to the electrodialysis tank is controlled to remove halogen ions, particularly bromide ions, from the developer by dialysis so that the concentration is kept constant; JP-A-54-3 discloses a continuous processing method in which the overflow liquid is further added with a deficient processing agent component and used again as a replenishing liquid.
No. 7731, No. 56-27142, etc.

(Problem to be solved by the invention) According to the ion exchange membrane electrodialysis method, continuous operation is possible.
Since it is also possible to adjust the halogen ions, this method has the advantage of being easier to handle and requiring less equipment space than the ion exchange resin method. However, in continuous processing using the above ion-exchange membrane electrodialysis method, when controlling the halogen ion concentration to be kept constant, fluctuations in current density, fluctuations in halogen detection accuracy, concentration of developer, etc. This causes a subtle 4-degree change in the halogen ions, which poses a problem in that the photographic performance (particularly sensitivity and gradation) obtained in continuous processing of silver halide color photographic light-sensitive materials is likely to fluctuate.

Furthermore, in a developer waste liquid regeneration system with a small amount of waste liquid,
By repeatedly reusing replenisher regenerated using ion exchange membrane electrodialysis, eluates from photosensitive materials can accumulate in the developer, and oxides such as developing agents and preservatives can accumulate in the developer. , and magenta sensitivity (especially D+ain).
) and the gradation tends to fluctuate significantly.

Therefore, it is an object of the present invention to provide a method for processing silver halide color photographic materials that can stably obtain excellent photographic performance in a development waste solution regeneration processing system using ion-exchange membrane electrodialysis. purpose.

Furthermore, the present invention provides excellent photographic performance (especially magenta sensitivity and U! ) It is an object of the present invention to provide a method for processing a silver halide color photographic light-sensitive material 4, which can stably obtain the following.

(Means for Solving the Problem) The above problem is achieved by processing a silver halide color photographic light-sensitive material that has been imagewise exposed with a color developer containing an aromatic primary amine color developing agent. 4 contains at least one pyrazoloazole magenta dye-forming coupler represented by the following general formula CI], and at least one layer containing the coupler contains 2 to 2 silver iodide.
It has been found that the problem can be solved by a method for processing a silver halide color photographic light-sensitive material, comprising a silver iodobromide emulsion containing 0 mol%, and characterized in that the color developer is subjected to an ion exchange membrane electrodialysis treatment. It was done.

General Formula [1] In the formula, X represents a coupling-off group, and L represents a hydrogen atom or a substituent. Ya, Wb and Yc each independently represent methine, substituted methine, 2N- or -Nil-, and either the Ya-Yb bond or the Yb-Yc bond is a double bond, and the other is a single bond. It is. Furthermore, R3 or X may form a dimer or more multimer. Further, when Va, Wb or 'lc is a substituted methine, the substituted methine may form a dimer or more multimer.

In particular, the total coating silver amount of the silver halide photosensitive material is 2 to 6 g/
When a mz photosensitive material is used, fluctuations in photographic properties due to running are stabilized, and excellent running performance can be obtained. Particularly preferred is a total coated silver amount of 2 to 4.5 g/m''.

The present inventors have conducted various studies on a method for regenerating silver halide color photosensitive materials using ion exchange electrodialysis. It has been found that the above problems can be solved by using a combination of an emulsion and a magenta coupler represented by the general formula [1].

The effect of the above combination in the regeneration process using ion exchange electrodialysis was completely unexpected and surprising.

The present invention will be explained in more detail below.

The silver halide color photographic light-sensitive material of the present invention contains at least one pyrazoloazole magenta coupler represented by the following general formula [1].

General formula (1) In the formula, X represents a coupling-off fin, and R1 does not represent a hydrogen atom or a substituent. Ya, Yb and Vc each independently represent methine, substituted methine 1. It represents either N- or -N11-, one of the Ya-Yb bond and the Yb-Yc bond is a double bond, and the other is a single bond. Furthermore, R1 or X may form a dimer or more multimer. Furthermore, when Ya, Yb or Yc is a substituted methine, the substituted methine may form a dimer or more multimer.

Preferable magenta couplers used in the present invention are represented by the following general formulas [11), [111) and (IV).

General formula (II) General formula CI[I) K! General formula (IV) In general formulas (1), [II), [111) and (IV), R8, R2 and R1 each independently represent a hydrogen atom or a substituent, and X represents a force or a bling leaving group. represent.

It*i in R1, R2 and R5 is preferably a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acylamino group, an anilino group, a ureido group, an imido group, Examples include sulfamoylamino group, carbamoyl group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, acyl group, alkoxycarbonyl group, carboxy group and hydroxy group.

More specifically, R1, R2 and R5 each independently represent a hydrogen atom, a halogen atom (e.g. chlorine, bromine), an alkyl group [e.g. methyl, ethyl, isopropyl, L-butyl, heptadecyl, allyl, methyl-2 -(2-hexadecyloxy-5-t-octylbenzenesulfonamido)ethyl], aryl group [e.g., phenyl, 2-methquinphenyl, 2.4-di-t-amyl phenyl, 2
4-dichlorophenyl, 23-'; chlorophenyl, 3
-(2-octyloxy-5-t-octylhenzenesulfonamido)phenyl], a heterocyclic group (e.g., 2-
furyl, 3-pyridyl, 4-pyridyl, l-pyrazolyl)
, alkoxy groups (e.g., metquin, ethoxy), butoxy, isopropyloxy, hexadecyloxy, 2-
Methoxoe I xy, 2-hexyloxyethoxy, 2
-phenoxyethoxy, t-butoxy, 24-diL-amylphenoxyethoxy, 2-ethylhexyloxy)
, aryloxy groups (e.g., phenoxy, 2-methoxyphenoxy, 24-dimethoxophenoxy, 26-dimethoxyphenoxy, 2-isopropyloxyphenoxy, 2-hexadecyloxyphenoxy, 2,4-di-t-amyl phenoxy, 2-pivaloylaminophenoquine, 2,4-dichlorophenoxy), heterocyclic oxy group (
For example, 2-henzimidapryloxy group), anrulamino group [e.g., acetylamino, henduylamino,
Tetradecanoylamino, pivaloylamino, 2-(2
, 4-di-L-amylfumatanoquine)hexanoylamino, 2-(4(4-hydroxyphenylsulfonyl)phenoquino)decanoylamino], anilino group (e.g., phenylanilino, 2-chloroanilino, N-acetylanilino) , 2-chloro-5-dodecyloxocarbonylanilino), ureido groups (e.g., phenylureido, methylureido, N,N-dibutylureido), imide groups (e.g., N-scunnimide, 3-henzylhydan)
・ynyl), sulfamoylamino group (e.g. NN-
dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), carbamoyl groups (e.g. N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-methyl-N-dodesol-rubamoyl), alkylthio groups ( For example, methylthio, butylthio, octylthio, tetrazotruthio, 2-phenoxyethylthio, 3-phenoxypropylthio), arylthio groups (e.g., phenylthio, 2-butylthio, 2-butylthio, 5-L-octylphenylthio, 3-pentadecylphenyl Thio, 2-
Carboxyphenylthio, 2-hexadecyloxy-5
-t-octylphenylthio), alkoxycarbonylamino groups (e.g. methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide groups (
For example, methanesulfonamide, hexadecanesulfonamide, p-toluenesulfonamide, 2-octyloxy 5-t-octylbenzenesulfonamide), acyl groups (e.g. acetyl, hendiyl), alkoxycarbonyl groups (e.g. methoxycarbonyl, butyloxy carbonyl, dodecyloxycarbonyl), carboxy group, or hydroxy group.

As R1 and R3, those in which methylene directly connected to the pyrazoloazole core is substituted and aryl groups are preferable.

-C In formulas (1) to [■], X represents a group capable of coupling with and leaving the oxidized developing agent, preferably an aryloxy group, an alkoxy group, an alkylthio group, an arylthio group, or an l-azolyl group. It is.

In more detail, 2-carboxyphenoxy, l-(fl.

1-dimethyl-1-(4-hydroxyphenyl))methylphenoxy, 4-(4-hydroxyhenzenesulfonyl)phenoxy, 4-methoxyphenoxy, 1-naphthoxy, 2-phenethyloxy, 5-phenyltetrazolyloxy, Arylokyne groups such as 2-hendithiazolyloxy; methoxy, ethoxy, isopropoxy, t-
Alcokyne groups such as butoxy, ethoxycarbonylmethoxy, 2-ethoxycarbonylethoxy, 2-cyanoethoxy, 2-methanesulfonylethoxy, 2-benzenesulfonylethoxy, 2-phenoxyethoxy; alkylthio groups such as dodecylthio and l-carboxydodecylthio; phenylthio, 2naphthylthio, 2-butoxy-
5-t-octylphenylthio, 2-pivaloylaminophenylthio, 4-dodecylphenylthio, 4-octyloxyphenylthio, 2-octyloxo-5-carboxyphenylthio, l-(3-carboxypropyloxy) -5-Arylthio groups such as 1-octylphenylthio; or 1-pyrazolyl, l-imidazolyl, 35-
Dimethyl-1241-riazol-1-yl, 5- or 6-furomohendazol-1-yl, 5-methyl 1,2,3,4-tetrazol-1-yl, 1-henzimidazolyl, 4-chloro -pyrazol 1-yl, 4-
1-Azolyl groups such as nitro-virazol-1-yl, 4-ethoxycarbonyl-pyrazol-1-yl, 3- or 5-acetamidopyrazol-1-yl, 2-acetamidoimidazolyl-1-yl. These may further have a substituent as indicated by R1.

Preferably, X is an aryloxy group, an arylthio group, or a 1-azolyl group, and more preferably, X is a substituted phenoxy group or a substituted pyrazol l-yl group.

When R1 is a secondary or higher alkyl group, X is preferably an aryloxy group; when R1 is an alkoxy group or an aryloxy group, X is preferably an arylthio group or a l-azolyl group.

When Pl, R2, R3 or 10-desolene group, CII□C11, -0
-C112C11□-1, etc.), substituted or unsubstituted phenylene u (e.g., 1,4-phenylene group, CIl,
C1 N11CO-R4-CONll- group (R4 represents a substituted or unsubstituted alkylene group or phenylene group, for example, 113 N1 (COCHiC1'bCONH-8-NIICOC
IIzC-C1hCONH-1C1l.

Represents a substituted or unsubstituted alkylene group, such as CH.

For example, -5-CIl, CH, -5-1-5-CH2C-C
H2-3-, etc.), and C11°X represents the above monovalent group converted into a divalent group at an appropriate position.

-G When the vinyl monomers include those represented by formulas (Il) to (IV), the linking group represented by R, R2, R5 or X is an alkylene group (substituted or unsubstituted alkylene group). , for example, methylene group, ethylene group, 1.1
0-decylene group, -ClhCHzOC1l□C1l□, etc.), phenylene group (substituted or unsubstituted phenylene group, e.g. Eva, 1.4-phenylene group, 1.3-)CONH
-1-o-, -oco-, and aralkylene groups (eg, groups formed by combining these groups).

Preferred linking groups include the following.

C0NII-CHzCIItN11CO~ , -C11
□CI+, 0-CIl, CIl□-NIICO The vinyl group may have a substituent other than those represented by the general formulas [ll] to [], and preferred substituents are a hydrogen atom, a chlorine atom, or a carbon atom. Examples include one to four lower argyl groups (eg, methyl, ethyl).

Monomers containing those represented by general formulas (n) to [IV) are copolymerized with an oxidized product of an aromatic-grade amine developer and a non-color-forming ethylene-like monomer that does not pull. Good too.

Examples of non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid,
α-chloroacrylic acid, α-alacrylic acid (such as methacrylic acid), and amides or esters derived from these acrylic acids (such as acrylamide, n-butylacrylamide, L-butylacrylamide, diacetone acrylamide, methacrylamide, Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, butyl acrylate, 1so-butyl acrylate, 2-ethylhexyl acrylate-1, n-octyl acrylate,
Lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β
-hydroxymethacrylate), methylenebisacrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylateryl, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene,
divinylhenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid,
Vinylidene chloride, vinyl alkyl ether (e.g. vinyl ethyl ether), maleic acid, maleic anhydride, maleic ester, N-vinyl-2-pyro IJ
Examples include F, N-vinylpyridine, and 2- and 4-vinylpyridine.

Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together. For example, n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and noacetone acrylamide, etc.

As is well known in the polymeric color coupler art, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers depend on the physical and/or chemical properties of the copolymer formed, e.g. solubility, compatibility of the photographic colloidal composition with binders such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred.

Next, specific examples of the coupler represented by the general formula [I] of the present invention will be shown, but the present invention is not limited thereto.

(Margin below) (1-2) on 6H13 (I 3) (1-4) ■3 Shi6H13 113 4119 (I 7) CI+.

(I 8) (1 11) (■ 12) (I 9) (1 10) H3 (1 13) (1 14) (1 15) 113 (1 16) (1 19) (I 20) (1 17) (1 18) し■3 し61113 (■ 21) (■ 22) (■ 23) (I 24) (1 27) (1 28) (I 25) (I 26) 'CsH+, (t) (I 29 ) (I 30) (I 32) (I 35) (I 36) p (1 33) (■ 34) (I 37) 113 1h (I 38) 113 113 (1 39) H3 C11゜0 COOCzlls H (I 40) 113 CI+3 (1 43) (■ 44) (I 41) C1 (3 113 (mol%) (■ 42) 113 C11゜A-Ctl t-Ch low-÷CHt C)〒- (1 45) ( I 46) all+7 (LJ (I 47) (■ 48) (I 51) (1 52) (1 49) (1 50) (+-53) (1 54) ■3 55) (1-57) 56) The magenta coupler of general formula [1] of the present invention is, for example,
It can be produced by the methods described in JP-A-60-197688, JP-A-61-053644, JP-A-62-209457, and the like.

The usage amount of the magenta coupler of formula (1) -a of the present invention is:
0.001 to 1 per mole of silver halide in photosensitive material
．． 0-El, more preferably 0.01 to 0.5 mol.

The magenta coupler additive layer of the general formula [1] of the present invention is:
Preferably, it is a light-sensitive silver halide emulsion layer or an adjacent non-light-sensitive layer. The light-sensitive silver halide emulsion layer is a green-sensitive silver halide emulsion layer, and when there are two or more green-sensitive layers, the magenta coupler of general formula [1) is added to at least one of the layers. Preferably, it is added to two or more layers, and most preferably, it is added to all of the green-sensitive layers.

In the present invention, when treating the developing solution by an electrodialysis method using an ion exchange membrane, any of the conventionally known electrodialysis methods using an ion exchange membrane used for processing photographic waste liquid can be used. can also be used. For example, Japanese Patent Publication Nos. 52-34939, 61-52459, 51-84636, 51-85722, 51
-97432, 52-119934, 53-1
No. 4933+, No. 53-46732, No. 54-962
No. 6, No. 54-19741, No. 53-7234, No. 52-146236, No. 52-143018, No. 5
The ion exchange membrane electrodialysis method described in each issue of No. 4-58028 can be used.

It is preferable to continuously lead the developer waste solution overflowing from the developer tank to the electrodialysis tank, treat it, and return the regenerated solution to the developer tank. It is also possible to temporarily store the developer waste liquid from the developer tank and process it in batches.

The electrodialysis tank has a plurality of demineralization chambers between the electrode chambers E by partitioning the electrodes by arranging a plurality of cation exchange membranes and a plurality of anion exchange membranes A in an alternating array of four. A structure in which a plurality of concentration chambers C and a plurality of concentration chambers C are alternately formed can be used.

The space between the cathode and the anode is alternately partitioned by cation exchange membranes and anion exchange membranes, and from the cathode side to the anode side there are a cathode chamber, multiple desalination chambers (the cathode side is a cation exchange membrane,
An ion exchange membrane electrodialysis tank consisting of a chamber (chamber partitioned by an anion exchange membrane on the anode side), multiple concentration chambers (chamber partitioned by an anion exchange membrane on the cathode side and a cation exchange membrane on the anode side), and an anode chamber. A developer waste solution is poured into the desalination chamber, a sodium sulfate solution or a sodium carbonate solution is poured into the alit chamber, and a direct current is passed between the negative and anode electrodes to perform electrodialysis.

However, in an electrodialysis tank with such a configuration, there are problems such as the concentration of the electrode solution decreasing depending on the type of membrane in contact with the electrode chamber, and the oxidation of bromide ions in the anode chamber. It is preferable to use an electrodialysis tank having the following configuration.

In this electrodialysis tank, the cathode and anode are alternately partitioned by cation exchange membranes and anion exchange membranes, and from the anode side to the cathode side there is an anode chamber, then a plurality of 'fj4 condensation chambers (the cathode side is the The anion exchange membrane, the anode side is divided by a cation exchange membrane) and the concentration chamber is the same number of demineralization chambers (the cathode side is divided by a cation exchange membrane, the anode side is divided by an anion exchange membrane). The demineralization chambers are arranged alternately so that the demineralization chambers are located farthest from the anode, and the cation exchange tIA
A concentration chamber separated by a membrane is provided, a cathode chamber is provided adjacent to the concentration chamber, and a common electrolyte solution is supplied and circulated to the cathode chamber and anode chamber. The a-condensation chamber liquid is passed through the condensation chamber.

Here, the anion exchange membrane and the cation exchange membrane may be any membrane as long as it has the ability to exchange anions or cations, and any exchange FIA membrane may be used within the scope of the present invention, but in particular the anion exchange membrane As the cation exchange membrane, a strongly basic type ion exchange membrane is preferable, and a strongly acidic type ion exchange membrane is preferable as the cation exchange membrane. Furthermore, as the anion exchange membrane, an exchange membrane that selectively permeates monovalent anions, particularly bromine ions and iodine ions, is desirable.

The electrode solutions used here include sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium phosphate, potassium phosphate, sodium nitrate, potassium nitrate,
Electrolyte solutions such as salts such as sodium bisulfate, sodium bicarbonate, alkalis such as potassium hydroxide, sodium hydroxide, acids such as sulfuric acid are suitable. It is sufficient that the concentration of these electrolyte solutions is 0.001N or more, and more preferably 0.01 to 2N.

These electrolyte solutions may optionally contain aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid or its sodium salt, ammonium salt, potassium salt; diethylenetriaminepentaacetic acid or its sodium salt; ethylenediamine-N-(βoxoethyl)-11,N ',N
'-triacetic acid or its sodium salt, ammonium salt; nitrilotriacetic acid or its sodium salt; triethylenetetraminehexaacetic acid or its sodium salt; or iminodiacetic acid), aminopolyphosphonic acid (e.g. 1.3 diaminopropano -Lou N, N, N', N
'-tetramethylenebosphonic acid, 2=phosphonobutane-
1,2,4 tricarboxylic acid, 1,3-propylenediamine-NNN, N-tetramethylenephosphonic acid or 1-hydroquino-ethane-1,1-diphosphonic acid, etc.), sodium hexametaphosphate, sodium i-ribolyphosphate,
Sodium pyrophosphate or 2-phosphoethylimino-N
, N-diacetic acid, etc. can also be added.

Electrolyte solutions containing salts such as sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium phosphate, potassium phosphate, sodium nitrate, potassium nitrate, sodium bisulfate, and sodium bicarbonate are suitable for the concentration chamber solution used here. ing. It is sufficient that the concentration of these electrolyte solutions is 0.001N or more, and more preferably 0.01 to 2N. This electrolyte solution may optionally include aminopolycarboxylic acid, aminopolyphosphonic acid, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, or 2-phosphoethylimino- N,N-diacetic acid and the like can also be added.

Furthermore, a corresponding developer waste solution may be used as the concentration chamber solution for regenerating the developer waste solution.

Materials for the cathode of the ion-exchange membrane electrodialysis cell include iron, nickel, lead, zinc, stainless steel, and the like, and materials for the anode include platinum, platinum, graphite, magnetite, and the like.

In addition, the current density applied to the ion exchange membrane electrodialysis of these developer waste solutions varies depending on the characteristics of the ion exchange membrane and the characteristics of the developer waste solution, but is generally O, lA/d to I
OA/dpo, more preferably 0.2A/dpo to 5A/dpo
It's d-po.

To regenerate the photographic developer using the ion-exchange membrane electrodialysis method of the present invention, the waste solution may be regenerated immediately before or at the same time as the waste solution is supplied to the desalting chamber of the dialysis tank.
6, No. 54-9626, No. 54-19741, No. 53132343, etc. Polymers, resins, various ion exchange resins (e.g., Diaion S^-1OA, 5A-2OA) , PA-316, P
A-418, -8-11, -A-20, CR-10,P
The method of the present invention also includes contact treatment of the waste liquid with an adsorbent such as Ni-220, PK-208, Shoolide 5-37, Amberlite IR-410).

In the method for regenerating photographic processing solution waste using the ion-exchange membrane electrodialysis method of the present invention, the processing solution waste discharged from the photographic processor is temporarily stored, and then the present ion-exchange membrane electrodialysis method (and in some cases This also includes the so-called Hatch method, in which halide ions, salts, silver, etc. are removed and recovered using a method (combined with an electrolytic method), and then a deficient treatment agent component is added and used again as a replenisher. Furthermore, as described in JP-A No. 54-37731, a constant bromide concentration is maintained while controlling the amount of current applied to the ion exchange membrane electrodialysis tank by detecting, for example, bromide ions in the photographic processing solution. This method also includes a so-called continuous regeneration method in which bromide ions are removed by dialysis, and only the deficient processing agent components are added to the waste processing solution discharged from the photographic processing machine to be used again as a replenisher.

Further, in order to perform electrodialysis while maintaining high current efficiency, the concentrated solution may be diluted with water as appropriate.

In particular, when using the above-mentioned continuous regeneration method, the concentrated solution is diluted with water to keep the concentration of halide ions, for example, bromide ions, in the concentrated solution constant within the range of 2 g/p (calculated as potassium bromide) or 20 g/n. Dilution is more preferred in order to keep the bromide ions in the developer constant to reduce fluctuations in photographic properties and to maintain high current efficiency for removing bromide ions from the developer. To replenish water for diluting this concentrated solution, for example, by operating the pump in synchronization with the replenishment pump that replenishes replenisher to the developer tank of an automatic processor, the amount of photosensitive material to be developed can be replenished. By replenishing water according to the amount of water, the bromide ion concentration in the concentrate is kept almost constant, the bromide ion concentration in the developer is more stable, and efficient dialysis can be maintained. More preferred.

In the former batch regeneration method, the bromide ion flux in the concentrate increases with the dialysis time, so the bromide ion concentration in the concentrate during dialysis is reduced to 2 g/f to 20 g/f (
It is preferable to replenish a certain amount of water using a pump to dilute the concentrated lily solution so that the amount of liquid (in terms of Br) is maintained.

On the other hand, as shown in Figure 2, the overflow liquid of the developer is usually stored in an overflow liquid stock tank, and when a certain amount has accumulated, it is transferred to a liquid preparation tank, where the missing components are added as a regenerating agent, and water is optionally added. It is possible to transfer the obtained solution to a replenisher stock tank and reuse it as a developer replenisher.

The regeneration method of the present invention includes bromide ions, chloride ions, sulfate ions, thiocyanine ions, sulfite ions, carbonate ions,
This effect can be exerted on all ordinary developing solutions containing at least two or more types of ions among phosphate ions, borate ions, nitrate ions, phosphonate ions, bicarbonate ions, and the like.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent.

A preferred example is a p-phenylenediamine derivative,
Representative examples are shown below, but the invention is not limited thereto.

D-IN, N-diethylnyl-phenylene diamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-CN-ethyl-N- (β-hydroquinethyl D=5 2-methyl-4-[N-ethyl-N[β-hydroxyethyl]amino]aniline D-6 4-amino-3-methyl-N-ethyl N-(β
-(methanesulfonamide)ethylcoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide rlJ-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N -ethyl N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl N-β-
Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl N-β-
Butoxyethylaniline Among the above p-phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferred.

Moreover, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and P-)luenesulfonate.

The amount of the aromatic primary amine color developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per 1f of color developer. As a preservative, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts can be added as necessary.

The preferable amount of preservative added is 0.5 per color developer if
g to 10 g, more preferably 1 g to 5 g.

In addition, as compounds that directly preserve the aromatic primary amine color developing agent, various hydroxylamines, hydroxamic acids described in JP-A-63-43138, and JP-A-63-43138 can be used.
- hydrazines and hydrazides described in No. 146041,
Phenols described in No. 63-44657 and No. 63-58443, α-hydroxyketones and α-aminoketones described in No. 63-44656, and/or No. 6
It is preferable to add various saccharides described in JP-A No. 3-36244, and in combination with the above-mentioned compounds,
No. 63-24254, No. 63-21647, No. 63-146040, No. 63-271341, No. 63-25654, etc.;
-30845, 63-14640, 63-43
Diamines described in No. 139 etc., polyamines described in No. 63-21647 and No. 63-26655, No. 6
Polyamines described in No. 344655, No. 63-5355
Nitroxy radicals described in No. 1, No. 63-43140
and alcohols described in No. 6353549, No. 63
Oximes described in No.-56654 and No. 63-239
Preferably, the tertiary amines described in No. 447 are used.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A No. 5 (i-9)
Polyethyleneimines described in No. 4349, U.S. Patent No. 3
, 746.544, etc., may be contained as necessary. Particularly preferred is the addition of an aromatic polyhydroxy compound.

The color developing solution used in the present invention preferably has a pH of 9 to
12, more preferably 9 to 11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pl+, it is preferable to use various buffers.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, 0-
Hydroquine sodium benzoate (sodium salicylate), potassium 0-1'oxybenzoate, 5-sulfo-2
Examples include 1.lium hydroxybenzoate (sodium 5-sulfosilycylate) and potassium 5-sulfol-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developing solution is 0.1 mol/I!
It is preferably at least 0.1 mol/l-0, particularly 0.1 mol/l-0,
Particularly preferred is 4 mol/IV.

In addition, various chelating agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or to improve the stability of the color developer.

The chelating agent is preferably an organic acid compound, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.

Specific examples are shown below, but the invention is not limited to these.

2I-lylotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1.2-diaminopropane tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid,
2-phosphonobutane-1,2,4 tricarboxylic acid, 1-
Hydroxyethylidene-1,1 diphosphonic acid, N, N'
-Bis(2-hydroxyhensyl)ethylenediamine-
N,N'-diacetic acid.

Two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer.

For example II! It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developing solution if necessary. However, it is preferable that the color developing solution of the present invention does not substantially contain Hensyl alcohol from the viewpoints of pollution, liquid preparation properties, and prevention of color staining. here"
"Substantially" means containing less than 2 d per developer, preferably not at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 451019 and U.S. Patent No. 3,8
Thioether compounds represented by No. 13.247, etc.
p-phenylenediamine compounds disclosed in JP-A-52-49829 and JP-A-50-15554;
Quaternary ammonium salts shown in Japanese Patent Publication No. 0-137726, Japanese Patent Publication No. 4430074, Japanese Patent Publication No. 56-156826 and Japanese Patent Publication No. 52-43429, etc., U.S. Patent No. 2,49
No. 4,903, No. 3.128.182, No. 4,230
, No. 796, No. 3,253.919, Special Publication No. 1977-1
No. 1431, U.S. Patent No. 2,482,546, No. 2,
Amine compounds described in Japanese Patent Publications No. 596,926 and No. 3.582゜346, etc., Japanese Patent Publication No. 37-16088, No. 42
-25201, U.S. Pat. Virapritons, imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of the organic antifoggant include hensitriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5methylhensitriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-henzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developing solution used in the present invention may contain a fluorescent whitening agent. As the fluorescent brightener, 4°4'-diamino-22'-disulfostilbene compounds are preferred. Addition amount is 0 to 5 g/l, preferably 0.1 g to 4 g/l
It is.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developing solution of the present invention is 20 to 50°C, preferably 30 to 45°C. The treatment time is 20 seconds to 5 minutes, preferably 1 minute and 30 seconds to 4 minutes. It is preferable that the amount of replenishment is small, but it is 100 to 2000 j per 1.12 photosensitive materials.
lf, preferably from 200 to 1500. More preferably, it is 300d to 1000-.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment.

The processing method of the present invention can also be used for color reversal processing. The black-and-white developer used at this time is a so-called black-and-white first developer used in the commonly known reversal processing of color photosensitive materials. Various well-known additives that are used in black-and-white developing solutions used in processing solutions for black-and-white silver halide light-sensitive materials can be included in the black-and-white first developer for color reversal light-sensitive materials.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone;
Preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, inorganic or organic agents such as potassium bromide, 2-methylbenzimidazole, methylbenziazole, etc. inhibitor of,
Water softeners such as polyphosphates, trace amounts of iodide,
Mention may be made of development inhibitors consisting of mercap-1 compounds.

In the present invention, used color developing solution (overflow solution)
contains a regenerating agent and reuses it as a color developer replenisher.

In principle, a regenerating agent is added to a used color developing solution (overflow solution) for the purpose of replenishing components consumed during color development processing.

The regenerant for color developer replenisher used in the present invention includes:
In principle, it contains the same type of color developing agent, ρ1111 buffering agent, and chelating agent as used in the color developing solution, as well as other components as necessary, such as preservatives, development accelerators, optical brighteners, etc. It is preferable that The amount of these drugs may also be set to compensate for the consumed components. The amount of these regenerants added is determined by the amount of regenerated replenisher obtained.
! The color developing agent is 0.001 to 0.02 mol, p
Hll buffering agent is 0, O1-0.2 mol, chelating agent is 0.
001 to 0.02 mol, and the preservative is preferably 0.01 to 0.03 mol.

In the present invention, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment tank with the air. Further, if necessary, concentration can be corrected by appropriately adding water when preparing a color developer replenisher for the amount of liquid evaporated in the developing bath.

In the present invention, desilvering treatment is performed after color development. Typical desilvering processes are shown below, but are not limited thereto.

1, (color development) - bleach-fix 2, () - bleach-fix 3, (〃) - bleach-bleach-fix 4, () constant-bleach-fix 5, () - bleach-bleach-fix 6, ( )-Bleach-fixing-Bleaching 7, ()-Bleach-fixing and fixing When the above desilvering step consists of two or more steps, a washing or rinsing bath may be provided between both steps. Further, an adjustment, water washing or stop bath may be provided between the color development step and the desilvering step.

In the above processing steps, each of the bleaching, bleach-fixing, and fixing processing baths may be a single bath, or may consist of two or more processing baths.The method for replenishing each processing bath is as follows:
Normally, the replenisher solution for each processing bath is replenished into the corresponding processing bath, but when the bleach-fix bath consists of multiple processing baths, the replenisher solution is added to the final bath and the overflow solution is added to the pre-bath. Replenishment may be carried out in a so-called counter-current manner, or in a so-called forward flow manner, in which a replenisher is added to the first bath and the overflow liquid is introduced into a subsequent bath. Further, in steps 3 and 4, the overflow liquid of the bleach bath or fixing bath, which is a pre-bath, can be introduced into the bleach-fixing bath to replenish the fixing component or the bleaching component to the bleach-fixing bath. Further, in step 5, the overflow liquid of the bleaching bath and the overflow liquid of the fixing bath may be respectively introduced into the bleach-fixing bath. Also, in steps 6 and 7, components of a subsequent bleach or fix bath may be introduced into the bleach-fix solution.

Bleaching agents for the bleach bath or bleach-fix bath of the present invention include:
Iron (m), cobalt (■), chromium (Vl) manganese (
(2), polyvalent transition metal ion compounds such as copper (It), peroxides, quinones, nitrobenzenes, etc. are used. For example, ferricyanide dichromate, iron (I [I) or cobalt (IV)]! Acid chelate compounds, ferric chloride, persulfates, hydrogen peroxide, permanganates, benzoquinone, and the like can be used. Among these compounds, it is preferable to use organic acid ferric complex salts from the viewpoint of pollution, safety, etc., and it is particularly preferable to use aminopolycarboxylic acid ferric complex salts. And examples thereof include the above compounds.

1, Ethylenediaminetetraacetic acid 2, Diethylenetriaminepentaacetic acid 3, Cyclohexanediaminetetraacetic acid 4, 1.2-Propylenediaminetetraacetic acid 5, Ethylenediamine-N-(β-oxyethyl)-N, N', N
'-triacetic acid 6, 1.3-diaminopropanetetraacetic acid 7, 1.4-
Diaminobutanetetraacetic acid 8, Glycol ether diamine tetraacetic acid 9, Iminoniacetic acid 10, N-methyl-iminoniacetic acid 11, Ethylenediaminetetrapropionic acid 12, N-(
2-acetamido)iminodiacetic acid 13, dihydroxydiethylglycine 14, ethylenediamine diorthohydroxyphenylacetic acid aminopolycarboxylic acid ferric complex salt may be used in the form of a complex salt, or as a ferric salt, e.g. ferric sulfate. , ferric chloride,
A ferric ion complex salt may be formed in a bath solution using an aminopolycarboxylic acid with ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. When used in the form of a complex salt,
A complex salt of l1llti may be used, 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 ferric ion complex.

Further, the bleach solution or bleach-fix solution containing the ferric ion complex described above may contain a metal ion complex salt other than iron, such as cobalt or copper.

The amount of these bleaching agents added is preferably 0.05 mol to 1 mol, particularly preferably 0.1 mol to 0.5 mol, per 12 of the bleach solution or bleach-fix solution.

The bleach or bleach-fix solutions of the invention may contain rehalogenating agents such as bromides, such as potassium bromide, sodium bromide, ammonium bromide, or chlorides, such as potassium chloride, sodium chloride, ammonium chloride. . In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid,
It may contain one or more inorganic acids, organic acids, salts thereof, etc., each having a pH buffering ability, such as sodium phosphate, citric acid, sodium citrate, and tartaric acid.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are found in U.S. Pat. No. 3,893.
No. 858, West German Patent Box No. 1.290,812, West German Patent Box No. 2,0
No. 59,988, JP-A-53-32736, JP-A No. 53-32736
No. 57831, No. 53-37418, No. 53-726
No. 23, No. 53-95630, No. 53-95631, No. 53-104232, No. 53-124424,
Compounds having mercap IJJ or disulfide groups described in JP-A No. 53141623, JP-A No. 53-28426, Research Disclosure NF117129 (July 1978); Thiazolidine derivatives described in JP-A-50-140129; 45-8506, JP-A-52-20832, JP-A-53-32735, U.S. Pat. No. 3,706,561; West German Patent Box 1,127,715, JP-A-Sho. 1623
Iodide salts described in No. 5; West German Patent No. 966, . No. 110,
Polyoxyethylene compounds described in Japanese Patent Publication No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others described in Japanese Patent Publication No. 49-42434 and Japanese Patent Publication No. 49-596.
Compounds described in No. 44, No. 53-94927, No. 54-35727, No. 55-26506, and No. 58-163940 can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in U.S. Pat.
The compound described in No. 0 is preferred.

Further preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the light-sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents in bleach-fix solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, especially thiosulfates. Ammonium sulfate is the most widely used. As the preservative for the bleach-fix solution, it is preferable to use sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds.

The pH of the bleaching solution or bleach-fixing solution of the present invention is not particularly limited, but when a ferric aminopolycarboxylic acid complex salt is used as a bleaching agent, the pH is preferably 3.0 to 8.0.

The amount of replenishment of the bleaching solution or bleach-fixing solution of the present invention needs to be changed depending on the amount of silver coated on the photosensitive material to be processed, but it is 1 (ld to 10001!) per 1@ of the photosensitive material!
1! is preferred.

The processing method of the present invention comprises processing steps such as color development, bleaching, bleach-fixing, and fixing as described above.

Here, after the bleach-fixing or fixing process, processing steps such as water washing and stabilization are generally performed, but after a bath with fixing ability, stabilization processing is performed without substantial water washing. A simple treatment method can also be used.

The rinsing water used in the rinsing step may contain known additives, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
Bactericidal agents to prevent the proliferation of various bacteria and algae, anti-fungal agents (for example, isothiazolone, organic chlorine disinfectants, hensitriazole, etc.), surfactants to prevent drying load and unevenness, etc. can be used. Also, L, E,
West.

“Water Quality Cr1teria
”, Phot, Sci, & Eng.

vol, 9. k6. pages 344-359 (
Compounds described in 1965) and the like can also be used.

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes the dye image is used. For example, a solution having a buffering capacity of pl+3 to 6, a solution containing aldehyde (for example, formalin), etc. can be used. The stabilizing liquid may contain ammonium compounds, metal compounds such as Bi and Af, optical brighteners, chelating agents (for example, 1-hydroxyethylidene 1,1-diphosphonic acid), bactericides, anti-fungal agents, Hardeners, surfactants, alkanolamines, etc. can be used.

Further, the water washing step and the stabilization step are preferably carried out by a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
, Mg6 degree 511g/j! It is preferable to use deionized water, water sterilized by halogen, ultraviolet germicidal lamp, etc. below.

In each of the above processing steps for color photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution may occur due to evaporation, especially when the processing amount is small or the opening area of the processing solution is large. It becomes noticeable. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step flows into a pre-bath having a fixing ability.

The light-sensitive material used in the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of the silver emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having a light-sensitive layer on a support, which is composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities; The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally as follows: A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order from the support side. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may contain color mixing inhibitors, ultraviolet absorbers, stain inhibitors, etc. as commonly used.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are
West German Patent No. 1.121.410 or British Patent No. 9
As described in No. 23,045, a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. −
No. 112751, No. 62-200350, No. 62-2
As described in No. 06541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side more disturbed than the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (B11) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (G1, )/high-sensitivity red-sensitive layer (R11)/low-sensitivity red-sensitive layer (RL), or BH/BL/GL/GH/RH/RL, or 1111/BL/Gll/GL/RL/ They can be installed in the order of R1+, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/Gll/
They can also be arranged in the order of IIH/GL/RL. Alternatively, as described in JP-A-56-25138 and JP-A-62-63936, the blue-sensitive layer/GL/RL/Gll/R1+ can be arranged in the order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with a lower sensitivity, and the lower layer is a silver halide emulsion layer that is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer with a low density is disposed and is composed of 3Ns having different photosensitivity, with the photosensitivity gradually decreasing toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

As mentioned above, the layer structure and arrangement of the gods can be selected depending on the purpose of each photosensitive material.

Any of these layer arrangements can be used as a color photosensitive material in the present invention.

Swelling rate of the photosensitive material used in the present invention [(25°C18,0
Equilibrium swelling membrane in 1￥-25'c, dry total film thickness at 55% R1+/dry total film thickness at 25°C, 55% RH) Xl
, OO) is preferably 50 to 200%, and 70 to 150%
% is more preferable.

If the swelling ratio deviates from the above-mentioned value, the photographic properties will be more susceptible to fluctuations.

Furthermore, the swelling rate of the photosensitive material used in the present invention is defined as a saturated film thickness of 90% of the maximum swollen film thickness reached when processed with a color developing solution at 30°C for 3 minutes and 15 seconds, and 17% of this saturated film thickness.
When the time required to reach 2 is defined as the swelling rate T, 72, it is preferable that T, 72 is 15 seconds or less.

More preferably, T172 is 9 seconds or less.

In the color photosensitive material #1 used in the present invention, at least one photographic emulsion layer containing at least one pyrazoloazole-based Mazenk dye-forming coupler represented by the general formula [1] contains 2 to 20 moles of silver iodide. % containing silver iodobromide emulsion. Particularly preferred is silver iodobromide containing from about 2 mole percent to about 10 mole percent silver iodide. Silver halide in other photographic emulsion layers is not particularly limited, but is preferably silver iodobromide containing about 20 mol % or less of silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 or less, or large grains with a projected area diameter of up to about 10, and the emulsion may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example,
Research Disclosure (RD), N.

17643 (December 1978), pp. 22-23, “
■ Emulsion preparation
on and types)”, same No. 18716 (
November 1979), p. 64B, and companion 30710
5 (November 1989>, pp. 863-865, Graphic “Physics and Chemistry of Photography”, published by Paul Montell) (
P. Glafkides.

ChemicetPhysiquePhoLograp
Hique, Paul Montel, 1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G
, F. Duffin, Photographic
Emulsion Chemistry, Foca
1 Press+ 1966), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al. 1, published by Focal Press (V,
L., Zelikman et al., Maki
ngand Coating Photography
c Emulsion, Focal Press,
(1964) and others.

U.S. Patent No. 3,574.628, U.S. Patent No. 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science and Engineering.
nce and Engineering), Vol. 14, pp. 248-257 (1970), U.S. Patent No. 4,
434.226, 4,414.310, 4,4
33,048, 4,439,520 and British Patent No. 2,112,157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may have a phase structure, and silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

In particular, in the present invention, the total coating silver amount of the silver halide photosensitive material is 2
6 g/m”, particularly preferably 2
~4.5 g/s". Furthermore, it is preferable that the total coating silver amount of the green-sensitive emulsion layer is 3 g/m" or less, and 2 g/s
``It is particularly preferable that the following is the case.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. The additives used in such processes are Research Disclosure No.
17643, same Nc, 1B716 and interval 3071
05, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the three research publications mentioned above, and the relevant descriptions are shown in the table below.

Various color couplers can be used in the present invention, and specific examples thereof include the above-mentioned Il[lN[L17643,
It is described in the patents listed in C-C and No. 307105, ■-C-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, 4,022.620, 4,326
, No. 024, No. 4,401,752, No. 4,248
, No. 961, Special Publication No. 58-10739, British Patent No. 1
, 425,020, 1,476.760, U.S. Patent No. 3.973,968, 4,314,023,
4,511,649, European Patent No. 249,473A
Preferably, those described in No.

As the magenta coupler, a pyrazoloazole magenta dye-forming coupler represented by the general formula [I] is used, but other magenta couplers may be used in combination as long as the effects of the present invention are achieved. As other magenta couplers, 5-pyrazolone compounds are preferred;
Those described in WO(PCT) 8B104795 and the like are preferred.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4.052.212.
No. 4,146.396, No. 4,228,233, No. 4.29 (i, No. 200, No. 2.369.929, No. 2,801.171, No. 2,772.162) issue,
2,895.826, 3,772,002, 3,758.308, 4,334,011, 4
, 327゜173, West German Patent Publication No. 3,329,72
9, European Patent No. 121.365A, European Patent No. 249.45
3A, U.S. Patent No. 3,446°622, U.S. Patent No. 4,33
No. 3.999, No. 4,753,871, No. 4゜451
．． No. 559, No. 4,427,767, No. 4,690,
No. 889, No. 4,254.212, No. 4,296.1
99, JP-A No. 61-42658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in Section 1-G of RD Sou 17643, U.S. Patent No. 4.
, No. 163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929, U.S. Pat. In addition, couplers that correct unnecessary absorption of coloring dyes from fluorescent dyes released during coupling described in U.S. Pat. No. 4,774,181, and U.S. Pat.
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in No. 20.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
．． 570, European Patent No. 96,570 and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820; 4,080,211;
4367.282, 4,409,320, 4
, 576.910, British Patent No. 2.102.173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is RD17643 as previously described.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
No. 63-37346, U.S. Patent No. 4.248.9
Preferably, those described in No. 62 and No. 4,782,012 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
Those described in JP-A No. 2,131,188, JP-A-59-157638, and JP-A-59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, etc., and U.S. Pat.
No. 4,338,393, No. 4,310,618, etc., JP-A-60-185950
DIR redox compound releasing coupler, DIR coupler releasing coupler DIR coupler releasing redox compound or DIR described in JP-A No. 62-24252, etc.
Redox-releasing redox compound, European Patent No. 173,
302A, a coupler that releases a dye that recovers color after giving up, RD Sou 11449, 24241, JP-A-6
Bleach accelerator-releasing couplers described in U.S. Pat. No. 1-201247, Gantt-releasing couplers described in U.S. Pat. 4,774,18
Couplers that emit fluorescent dyes as described in No. 1 can be mentioned.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high-boiling point solvents used in the oil-in-water dispersion method are described in U.S. Patent No. 2,322.027, etc.; As a specific example of the solvent, phthalate ester 1!
(dibutyl phthalate, dicyclohexyl phthalate,
Di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate,
bis(2゜4-di-monoamyl phenyl) isophthalate, bis(l,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl) Diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate,
tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters 14 (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate) ), amides [(NN-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols 1! (isostearyl alcohol, 2,4-te
rt-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.)
, aniline derivative (N,N-dibutyl-2-butoxy-5
-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, the boiling point is about 30°C or more, preferably about 50°C or more, about 160°C.
An organic solvent having a temperature of 0.degree. C. or lower can be used, and typical examples include ethyl acetate, bunal acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation are disclosed in U.S. Pat. No. 4,199,363, West German Patent No.
, 541°230, etc.

These couplers can also be impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. W 08B100723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

The present invention can be applied to various color photosensitive materials. It is particularly preferable to apply the present invention to color negative films for general use or movies, and color reversal films for slides or televisions.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
, D, page 28 of k17643, and N111871
6, from the right side of page 647 to the left column of page 648.

(Example) The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these.

Example-1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of the photosensitive layer) The coating amount is expressed in root g/nT for silver halide and colloidal silver, and the amount expressed in g/rrf for coupler additives and gelatin. The number of moles of the dye is expressed per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver ...0.15
Gelatin ・・・・・・1.5E
x M -8...0.08LI V -1・-
...0.03 UV-2...0.06 S o I v -2--" 0.08UV-3.
...0.07 Cpd-5...6XIO-'2nd layer (middle layer) Gelatin ...1.5UV
-1...0.03 Ul-2...0.06 UV-3...0.07 Ex F -1---0,004 S o l v -2--0,07 Cpd-5...6X10-' Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (Agl 2 mol%, internal high Agl type, equivalent sphere diameter 0.34, coefficient of variation of equivalent sphere diameter 29%, normal crystal,
Twinned mixed grains, diameter/rg ratio 2.5) Coated silver amount...
...0.5 Gelatin ...0.8Ex
S-1...1. OX 10-'Ex S-2・
--3,0XIO-' ExC-3... 0.22 ExC-4... 0.02 Cpd-5... 3X10 -'4th layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (8 g + 4 mol%, internal high Agl type, equivalent sphere diameter 0.55 m, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin Crystal mixed particles, diameter/thickness ratio 1) Coated silver amount...
・0.7 Gelatin ・・・1.26E
xS-1...lXl0-' Ex S-2-3X10-' ExC-3...0.33 Ex C-4・----・0.01 ExY-12...0. OI Ex C-7-=・0.04 ExC-2...0.08 S o l v-1-0,03 Cpd-5...5X10-' 5th layer ( Third red-sensitive emulsion layer) Silver iodobromide emulsion (Agl 19 mol%, internal high Agl type,
Equivalent sphere diameter 0.7-1 Coefficient of variation of equivalent sphere diameter 30%, twin grains, diameter/thickness ratio 2) Coated silver amount...0.7 Gelatin...0.8E x
S -1-lXl0-' Ex S-2-3X10-' Ex S-3・=-IXIO-' Ex C-5-=・0.05 Ex C-6--------0 ,06 S o I v -1・-= 0.15 S o I v
-2・----0,08Cpd-5・・・・・・3
X 10-' 6th layer (middle layer) Gelatin 1.0Cpd-54
X10-' Cpd-10,10 Cp d -41,23 Solv-10,05 Cpd-30,25 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (8g 12 mol%, internal high Agl type , sphere equivalent diameter 0.3mm, f, coefficient of variation of F equivalent diameter 28%, normal crystal, twin crystal mixed grain, diameter/I yen ratio 2.5) Coated silver amount...
...0.30 Gelatin ...0.4E
x S-4+・++++ 5XIO-'E x S-
6-0,3X10-' E x S -5--2XIO-' E x M -9----0,2 E x Y -11...0.03ExM-8・
...0.03 S o l v -1-0,2 Cpd-5...2'X] C1-' 8th layer (second green emulsion layer) Silver iodobromide emulsion ( Agl 4 mol%, internal high Agl type, equivalent sphere diameter O, SS*, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twinned mixed grain, diameter/thickness ratio 4) Coated silver amount...
・0.6 Gelatin ・・・・・・0.8E
x S-4...5X10-'E x S-5・
...2X10-'E x S-6...=0.3x
lO-'E x M -9=----0,25 E x M-8=----0,03 E x M-10...0.015 F, x Y-11=- ...0.04 So 1v-1-=-0,2 Cpd-5...3X10-' 9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 10 mol%, internal High Agl type,
Ball equivalent diameter 0.7t! m, coefficient of variation of equivalent sphere diameter 30%, normal crystal, twin crystal mixed grain, diameter/thickness ratio 2.0) Coated silver amount・
...0.85 Gelatin ...1.0E
x S -4=----2,0X10-'ExS-5・
...2.0X10-'E x S-6---0,
2XIO-'Ex S-7-...3.0xl
O-'E x M -9・--0,07 E x M-8・---0,02 S o l v -1...0.20S
o l v -2-0,05 cpct-5...4XIO-'10th layer (I-filter layer) Gelatin...0.9 Yellow colloidal silver...・0.05Cp
d-1...0.2 S o I v -1-0,15 Cpd-5...4XlO-' 11th layer (first blue emulsion layer) Silver iodobromide emulsion (Agl 4 mol%, internal height GL type, spherical equivalent diameter 0.5-1 spherical equivalent diameter variation coefficient 15%, octahedral particles) Coated silver amount: 0.4 gelatin
・・・・・・1. OE x S -8-
---2X10-'E x Y -12----・-・0
．． 9ExY -11...0.09 Solv-1...0.3 Cpd-5...4X10-' 12th layer (2nd
Blue-sensitive emulsion layer) Silver iodobromide emulsion (Agl 10 mol%, internal high Agl type,
Equivalent sphere diameter], 31M, coefficient of variation of equivalent sphere diameter 25%, normal crystal, twinned mixed grains, diameter/thickness ratio 4.5) Coated silver amount...
...0,5 Gelatin ...0,6E
x S-8...lXl0-'E x Y-12
=・-0,12 Solv-1...0,04 Cpd-5...2X10-' 13th layer (first protective layer) Fine grain silver iodobromide (average grain size 0. 01n, Agl 1 mol%) ...0.2 Gelatin ...0.8tJ
V-3:...0.1 UV-4...0.1 UV-5...0.2 S o I v-3-0,04 Cpd-5 ...3X10-' 14th layer (second protective layer) Gelatin ...0.9 polymethyl methacrylate particles (diameter 1.5I1m) ...0.2Cpd -5・
...4XlO-' 11-1 ...0.4
In addition to the above ingredients, a surfactant was added to each layer as a coating aid. Sample I4 produced as described above was designated as sample 101.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

(Margin below) UV l: 5olv-1 ni tricresyl phosphate UV 2: ol ■ 2: Diptyl phthalate +1fl ol ■ 3: bis phthalate (2 ethylhexyl) ExS l: zHs UV 3: ExS 2: UV 4: C2II=.

113 -(CH2-Chr-HCHI C11゜ 1 COOCHzcHzOco 0OCH3 N x/y=7/3 (weight ratio) ExS-3: ExS 7: zHs Cz II s ExS 4: zHs ExS 8: ExS 5: C, +1.

pd 1: Ci, lI+z(n) ExS-6: C□11゜ C611B(n) (1,, Nt)a≧υkoh Cpd 4: xF 1: C2)+5 C2IIs xC 5: 'C, II +([) Imi χC 6: Leaf xC 7: υ CI+□ xC 2: Leaf xC 3: 01( xC 4: 11 xM 8: l xM 9: 1h COOC411,.

mol, wt.

Approximately 20,000 ExM 10: ExY-12: 1 ExY-11: 113 CH3 H-1: CIl□-CH-5O□-CIl□-CONII -C
I+□CIl□-CH-5O□-CH2-C0NII-
CI+□Next, the magenta coupler ExM-9 used in the 7th to 9th layers of sample 101 was changed to the coupler shown in Table 1 (equimolar to ExM-9), and further the magenta coupler ExM-9 used in the 7th to 9th layers
The silver iodide content of the silver iodobromide emulsion used in the layers (first to third green-sensitive emulsion layers) was changed as shown in Table 1, and samples 102 to
106 was created.

Table 1 Samples 101 to 106 prepared as above were subjected to imagewise exposure, and while the color developer was regenerated using a small automatic developing machine, the color developer was replenished by the method detailed below. Processing was maintained until the volume was three times the capacity of the color processing tank.

Processing process Processing time Processing temperature Replenishment 1i"'t'
) Capacitive color development 3 minutes 15 seconds 3B, 0°C 600 resistance 7! Bleach 50 seconds 38.0°C
130*E 5p bleach fixing 50 seconds 38
．． 0'c---5p fixation 50 seconds 3
8.0°C 415mN 5N water washing (])
330 seconds 38.0°C□ 31Wash (2)
20 seconds 38.0"C880mN 31 stable
20 seconds 38.0°C520*E 3E drying 1 minute
The amount of replenishment at a rate of 55°C was the amount per photosensitive material #41.The washing water flowed in a countercurrent manner from (2) to (1), and all the overflow of the washing water was introduced into the fixing bath.

The bleach-fixing bath can be refilled by connecting the top of the automatic processor's bleach tank and the bottom of the bleach-fixing tank, and the top of the fixing tank and the bottom of the bleach-fixing tank with pipes, and supplying replenisher to the bleach tank and fixing tank. All of the overflow liquid generated was allowed to flow into the bleach-fix bath.

The amount of developer brought into the bleaching process, the amount of bleach brought into the fixing process, and the amount of fixer brought into the washing process are 2.5 d and 2.0 d per 1 meter length of the photosensitive material of 3511+111, respectively. , 2.0m.

Further, the crossover time is 5 seconds in each case, and this time is included in the processing time of 111 culms.

The composition of the treatment liquid is shown below.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1-hydroxyethylidene 1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 2-Methyl-4-(N- Ethyl-N-(β-hydroxyethyl)aminocoaniline 2.0 2.2 3.3 3.3 3.9 37.5 1.4 1.3ffig 2.4 4.5 5.2 39.0 0 .4 Add sulfate water to pH (bleach solution) 1, Of 1.1 10.05 10.15 Mother liquor (g) Replenisher solution (g) 13-Propylenediamine 144.0 206.0
Ferric ammonium tetraacetate monohydrate ammonium bromide 84.0 120.
0 Ammonium nitrate 17.5 25
．． 0 hydroxyacetic acid 63.0 90
．． 0 Acetic acid 33.2 47.4 Add water 1.1! 1.0
ffpH (prepared with ammonia water) 3.20
2.80 (Bleach-fixing solution mother liquor) A 15:85 mixture of the above bleaching solution mother liquor and the following fixing solution mother liquor.

(Fixer) Mother liquor (g) Ammonium sulfite 19.0 Replenisher (g) 57.0 8 liquids of ammonium thiosulfate water (Add 700 g of imidazole ethylenediaminetetraacetic acid water and pl ([ammonia water, adjustment]) (Washing water ) Common tap water for mother liquor and replenisher was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and 011-type strong basic anion exchange resin (same Amberlite IP^-).
Water was passed through a hot bed column packed with 400) to reduce the concentration of calcium and magnesium ions to 3 mg71 or less, followed by 20 mg of 1-lium isocyanurate dichloride.
/l and 150 mg/l of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing solution) Mother solution and replenisher common 85.5 37.5 1, Of 7.45 840 m! 28.5 12.5 1.0! 7.40 80d With acetic acid (unit: g) Formalin (37%) 2,〇-Polyoxyethylene-p-mono 0.3 Nonyl phenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium 0.05 Lium salt water In addition 1.0ppH5
, 0 to 8.0 The color developer was regenerated by the ion exchange membrane electrodialysis method described below.

10 strong basic anion exchange membranes and strong acidic cation exchange membrane I
The color developer tank is connected to the desalting chamber of the ion exchange membrane electrodialysis tank, which has 12 sheets of A 1lff (2 dm2 each), stainless steel cathodes, platinum metal anodes, and an array of stainless steel cathodes and platinum metal anodes, to circulate the color developer. did.

In the concentration chamber of the dialysis tank, a solution obtained by diluting the color developer shown above four times with water was circulated. Further, in the electrode chamber of the dialysis tank, the following electrolyte solution was circulated in both the cathode chamber and the anode chamber.

(8 solutions of electrolytes) Sodium carbonate 29.3g Sodium bicarbonate 6.4g Sodium ethylenediaminetetraacetate 1g Add water
1000III (pH 10, 20) The amount of electricity passed between the negative and positive poles of this dialysis tank is 0.6 to 3.
Continuous processing was carried out while keeping the potassium bromide concentration in the color developer at 1.4 g±0.05 g by adjusting it within the range of A/2 dm2.

In addition, a processing agent necessary for reuse as a replenisher was added to the overflow liquid from the color developing tank of this automatic processor, and the replenisher was used repeatedly. A conceptual diagram of the system is shown in FIGS. 1 and 2.

Samples 101-106 were imagewise exposed using the above method while regenerating the color developer using the ion exchange lI9 electrodialysis method until the replenishment amount of the color developer became three times the capacity of the color development processing tank. were processed continuously.

Before and after the continuous processing, each of the samples 101 to 106 was subjected to gradation exposure for sensitometry, and then processed.

Changes in magenta sensitivity (density at an exposure amount of minimum density + 0.2) and magenta gradation (from the point representing density 0.5) in the sensitometry before and after continuous processing
Changes in density (density difference up to the density point on the high exposure side of 2.0 at ogE) were measured, and the results are shown in Table 2.

Table 2 As is clear from Table 2, when a magenta coupler other than the present invention is used or an emulsion other than the present invention is used, regeneration using ion exchange membrane electrodialysis method results in magenta sensitivity. and the change in gradation is significantly large.

On the other hand, when the magenta coupler of the present invention is used in combination with the emulsion with the silver iodide content of the present invention, it is stable even in a treatment method in which the amount of waste liquid is significantly reduced by regeneration using ion exchange membrane electrodialysis. It can be seen that the rotation performance can be maintained.

Example-2 On a subbed cellulose triacetate film support,
A multilayer color photosensitive material 201 was prepared by coating each layer having the composition shown below with a heavy nitrogen coating.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in units of g/m2, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 0.40 2nd layer (intermediate layer) 2.5-G[-pentadecylhydroquinone 0.18EX-10
,07 E (
1st red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.6
-1 Variation coefficient regarding particle size 0.15) Silver 0.55 G, 9X10-5 1.8 X 10-5 3,]X]0-'4.0X10-' 0.350 0.005 Sensitizing dye I Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ X-2 BS-1 E X -100,020 Gelatin 1.20 4th layer (
2nd red-sensitive emulsion layer) Tabular silver iodobromide emulsion (iodide vA 10 mol%, average grain size 0
, 7-1 average aspect ratio 5.5, average thickness 0, 2
ta) Silver 1.0 increase r9
Pigment! 5. lXl0-' Sensitizing dye II 1.4 X 10-
5 sensitizing dye” 2.3XIQ-
4 Sensitizing dye IV 3. OXI
Q-5EX-20,400 EX-30,050 EX-100,015 Gelatin 1.30 5th layer (
Third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 16 mol%, average grain size 1, IJ/
11) Silver 1.60
Sensitizing dye IX 5.4 x 1
0-' Sensitizing dye It 1.4X
10-' Sensitizing Dye I [12,4X 10-' Sensitizing Dye IV 3. lX1O-
5E Sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.6
Voice, average aspect ratio 6.0, average thickness 0.15-)
Silver 0.40 sensitizing dye V3.0xl
O-' Sensitizing dye Vl 1.0X10-
'Aggravating pigment■ 3.8xlO-'
EX -60,260 EX-10,021 0,040 0,020 0,004 0,80 E 75 8th layer (second green-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 9 mol%, average grain size 0.7
-1 Coefficient for particle size 0.18) Silver 0.80 2, lXl0-5 7, OX 10-5 2.6X10-' 0.180 0.010 0.008 0.012 0.160 0.00B 1. 10 Sensitizing dye V Sensitizing dye■ Sensitizing dye■ X-5 X-8 X-I (Silver iodide 12 mol%, 1.0 mol%) Silver sensitizing dye■ Sensitizing dye■ Sensitizing dye■ X-6 EX-11 X-1 HB S-1 B5-2 Gelatin 10th layer (yellow filter layer ) Yellow colloidal silver X-5 II B S-3 Gelatin 11th layer (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (iodide vA 6 mol %, average grain size 0.
6IJ@, average aspect ratio 5.7, average 0.05 0.08 0.03 0.95 average particle size 1.2 3.5xlO-5 8,0xlO-5 3, Ox 10-' 0.065 0, 030 025 0.25 0.10 1.74 Silver thickness 0. 15pH Silver 0.24 Multiplying dye■ 3.5XlO~4■
Mi X-90,85 L", , average particle size 0.
ha, coefficient of variation regarding particle size 0.16) Silver 0.45 Sensitizing dye■ 2.1X10-'E
X-90,20 E ,3
trm) Silver 0.77 Sensitizing dye■ 2.2X]O-'EX
-90,20 HB S -10,07 Gelatin 0.69 No. 14N
(First protective layer) Silver iodobromide emulsion (silver iodide 1 mol%, average grain size 0.07 cells)
Silver 0.5U-40,11 U-50,17 HB S -10,90 Gelatin 1.00 15th layer (second protective layer) Polymethyl acrylate particles (diameter approx. 1.5s) 0.54S
1 0. +53-2
0.05 gelatin
0.72 In addition to the above ingredients, each layer contains
Gelatin hardener 1-(-1 and surfactant were added.

(Left below) -5 10 X 113 C11゜-(CIl
, CH20CO 0OCH3 X 11 N x/y=7/3 (weight ratio) (i) C411,0CNH 1 EX 8 EX EX EX EX EX lli 11 H CH.

EX C11゜ C00C,H.

EX fl/ EX-10 11 CI+.

EX 11.EX Same as 1, However, R is Ho EX 2 2115 C.H.

CZH50SO3e S ■ sensitizing dye BS 1; tricresyl phosphate B.S. 2; dibutyl phthalate 1 B S 3; Screw (2 ethylhexyl) lid 1 note ■ C,H.

CL=CI+ SO□ th 0N11 112 CH2=C11 O2 H2 C0NI+ C11□ zHs ~′ Cz II s ■ Ct II.

■ Cz tl s ■ C, +1.

l Cz It.

(For UHtJ 4bU3, the magenta coupler Ex-G used in the 7th to 9th layers of sample 201 was changed to the magenta coupler shown in Table 3,
Samples 202 to 21 were prepared in the same manner except that the amount of coated silver halide in layers 7 to 9N was changed as shown in Table 3.
0 was created.

Table 3 Samples 201 to 210 prepared above were each subjected to imagewise exposure and continuously processed in the following processing steps using an automatic processor.

Processing process Processing time Processing temperature Replenishment amount 0 Kunk capacity color development 3 minutes 15 seconds 38°C 45d lOR bleach 1 minute 00 seconds 38°C 20d 4f bleacher 3 minutes 15 seconds 38°C3Qmffi 87
! 30aj! 4F 20 Company 41 Washing (2) 1 minute 00 seconds 35°C Stable 40 seconds 38°C Drying 1 minute 15 seconds 55°C *The amount of replenishment is per 1 meter length of 35 mm Next, write down the composition of the treatment solution. .

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid l-hydroxyethylidene 11-diphosphonate Sodium sulfite 1.0 3.0 4.0 1.1 Potassium carbonate Potassium bromide Potassium iodide Hyaloxyamine Sulfate 4-(N-ethyl-N-β-hydroxyethylamino)-2 Add methylaniline sulfate water and pl+ (bleach solution) Common to mother liquor and replenisher ethylenediaminetetraacetic acid ferric ammonium trihydrate ethylenediaminetetraacetic acid di Sodium salt ammonium bromide ammonium nitrate bleach accelerator 30.0 1.4 1.5 mg 2.4 37.0 0.7 2.8 4.5 5.5 ], 01 1.0ff 10.05 10.10 (unit g) 120.0 10.0 100.0 10.0 0.005t ammonia water (27%) 15.
Add 0mN water 1.0
ppH 6,3 (Bleach-fix solution) Common to mother liquor and replenisher (Unit g) Ethylenediaminetetraacetic acid ferric ammonium trihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Thio G7L
fi1 ammonium aqueous solution (700g/l)
240.0mR ammonia water (27%) Add 6.0m water 1. OIV.

pH 7.2 (washing solution) Common tap water for mother liquor and replenisher was mixed with 11-type strongly acidic cation exchange resin (Amberly R-120B manufactured by Rohm and Haas) and 011-type strongly basic anion exchange resin (same Amberly IIRA). −
Water was passed through a mixed bed column packed with 400) to reduce the concentration of calcium and magnesium ions to 3 mg/l or less, followed by 20+ mg of sodium incyanurate dichloride.
/A and 0.15 g/i of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit g) Formalin (37%) 2.0 Female polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disl-lium salt Add 0.05 water to 1.0ffpH
5.0 to 8.0 For the above processing, the color developer is recycled by applying the ion exchange resin method and the ion exchange membrane electrodialysis method according to Table 4, and the replenishment amount of the color developer is The imagewise exposed samples 201 to 210 were continuously processed until the volume reached three times the capacity of the processing tank.

The ion exchange membrane electrodialysis method was performed in the same manner as in Example-1.

The ion exchange resin method was performed as shown below.

The overflow liquid generated by replenishing the color developer with 10 f is treated with anion exchange resin (Amberlite IRA- manufactured by Rohm and Haas), which has been previously treated as follows.
400) The solution was passed through a plastic cylindrical column filled with 10 N at a rate of 200 d/min and collected.

Hydroxylamine, sodium sulfite, and 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate in the recovered liquid were quantitatively determined, and water was added. It was prepared and regenerated so as to have the above-mentioned replenishment composition.

The solution regenerated in this way was used as a replenisher from now on, and
Each time 1 was replenished, it was regenerated and used in the same manner as above.

*First treatment of anion exchange resin: 0.5M/N sodium bicarbonate solution l
OP is passed through the column at a rate of 100 sf per minute, followed by distilled water (H!) at a rate of 200 ml per minute for washing.

2nd time onwards: After using to regenerate the developer, distilled water 10i! was washed by passing liquid through it at a rate of 200 d/min, and was further washed in the same manner as the first time.

As in Example-1, the above 47 (1
Each of Nos. 4201 to 210 was subjected to tone exposure for sensitometry, processed, and magenta sensitivity changes and tone changes were measured. The results are shown in Table 4.

(Left below) As is clear from Table 4, when the magenta coupler of the present invention is not used, there is no change in photographic properties even if the color developer is reused using the ion exchange resin method and the ion exchange membrane electrodialysis method. Large (Experiment No. 1.2.5.6.7).

Furthermore, even when using the magenta coupler of the present invention,
When using the ion exchange resin method, there is a large variation in photographic properties (
Experimental Na3.4).

On the other hand, according to the configuration of the present invention, it can be seen that the application of the ion exchange membrane electrodialysis method has an excellent improvement effect (Experiments Nα8 to Nα14).

Furthermore, it is found that in the present invention, it is particularly preferable that the total coating amount of the magenta coloring layer is 3.0 g/nf or less (Experiment No. 14 vs. Experiment Nc12.13).

(Effects of the Invention) In a method of processing an imagewise exposed silver halide color photographic light-sensitive material with a color developer containing an aromatic primary amine color developing agent, the amount of replenishment of the color developer can be reduced, and When color developer waste was recycled, the obtained photographic properties (sensitivity and UR) varied, and stable photographic properties could not be obtained. In particular, variations in magenta sensitivity and gradation were remarkable.

In the processing method of the present invention, the photosensitive material 4 contains at least one specific pyrazoloazole magenta coupler, and at least one of the layers containing the coupler contains a specific iodobromide compound having a high silver bromide content. Since it is made of a silver emulsion and the color developer is subjected to ion exchange membrane electrodialysis treatment, fluctuations in magenta sensitivity and gradation can be suppressed to a small level.

Therefore, in the present invention, the amount of developer waste liquid discharged can be reduced.

[Brief explanation of drawings]

FIG. 1 shows a conceptual diagram of an electrodialysis device used in the present invention, and FIG. 2 shows a conceptual diagram of the connection between the color developer tank and the electrodialysis device and how to reuse the color developer replenisher. (Symbols in the figure) A... Anion exchange membrane K... Cation exchange membrane D... Demineralization chamber C... Concentration chamber E... ...Electrode chamber N1...Color developer N1-R...Color developer replenisher box 1 Figure

Claims (1)

[Scope of Claims] In a method of processing an imagewise exposed silver halide color photographic light-sensitive material with a color developer containing an aromatic primary amine color developing agent, the light-sensitive material has the following general formula [
contains at least one pyrazoloazole magenta dye-forming coupler represented by I], at least one layer containing the coupler consists of a silver iodobromide emulsion containing 2 to 20 mol% of silver iodide, and A method for processing a silver halide color photographic material, characterized in that the color developer is subjected to an ion exchange membrane electrodialysis treatment. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents a coupling-off group, and R_1 represents a hydrogen atom or a substituent. Ya, Yb and Yc each independently represent methine, substituted methine, =N- or -NH-, one of the Ya-Yb bond and the Yb-Yc bond is a double bond, and the other is a single bond. It is a combination. Furthermore, R_1 or X may form a dimer or more multimer. Further, when Ya, Yb or Yc is a substituted methine, the substituted methine may form a dimer or more multimer.