JPH02203339A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To inhibit changes in sensitivity and fog and the deterioration of the shelf stability of an image and to practically prevent the discharge of a color developing soln. by bringing the color developing soln. used to process a color photographic sensitive material contg. at least one kind of specified pyrazoloazole type magenta coupler into contact with an anion exchanger and reusing the developing soln. CONSTITUTION:When a color developing soln. is regenerated with an anion exchanger, at least one kind of pyrazoloazole type magenta coupler represented by formula I is incorporated into a silver halide color photographic sensitive material to be processed. In the formula I, R1 is H or a substituent, X is H or a group which is released by a coupling reaction with the oxidized product of an arom. prim. amine developing agent and each of Za-Zc is methine, substd. methine, =N- or -NH-. Even when the color developing soln. is repeatedly regenerated with the anion exchanger and used over a long period of time, superior shelf stability of an image can be ensured and a load of a waste soln. and control work are reduced.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for processing silver halide color photographic materials and optical materials, and in particular, it reduces the amount of waste liquid by recycling the color developing solution, and also reduces the amount of halogen The present invention relates to a method for processing a silver halide color photographic material, which allows the silver halide color photographic material to maintain stable finishing performance and excellent image storage stability.

(Prior art) In recent years, since environmental pollution caused by sedentary wastewater has become a problem, various efforts have been made to reduce the amount of wastewater in the processing of photographic materials in order to reduce the pollution load. . Among them, the most important issue was to reduce the amount of color developing solution discharged, which has a large BUD (biological oxygen demand 1) and C0D (chemical oxygen demand) load. Up to now, roughly λ methods have been proposed to address this problem. 7 is a method called a low replenishment processing method that reduces the amount of replenishment of the color developer while preventing a decrease in color development activity by increasing the color development processing temperature; This is a method called a reprocessing method in which all accumulated halogens are removed from the film, the development activity is restored, and the film is reused.

The former compensates for the decrease in developer activity due to the accumulation of halogen ions such as iodine ions, bromine ions, and chloride ions released from the photosensitive material during development by increasing the temperature, pH, and color developing agent. Although simple, there are limits to compensation, and it is difficult to reduce replenishment tt to a large extent and approach zero emissions.

The latter regeneration treatment method is described in Journal of the SMPTE Vol. 4j, l as a means of removing accumulated halogen ions.
A7g page~≠r4t (/Riyo 6, February issue) There is an anion exchange resin method described in K and an electrodialysis method described in JP-A-32-//Tata No. 341, both of which require special Although it has the disadvantage of requiring equipment, research has been progressing as a method that can eliminate the discharge of color developer.

In particular, methods using anion exchange resins are less effective than electrodialysis.
Because the cost of the device is low, it has been put into relatively wide use, and its use has also been reported in the Journal of Applied Photographic Engineering! Volume, /16
A method for completely preventing performance deterioration of an anion exchange resin by treating a color developing solution pretreated with an adsorbent with an anion exchange resin, as described in μ, page 276 ~ 2/Tavage (2017, Autumn issue). , Journal of Image Technology Vol. 13, /163.13 describes improvements such as the development of a miniaturized system that makes anion exchange resin disposable, as described in Jill 1r page 9 (/917, June issue). Research is underway.

However, when color developing solutions are repeatedly reused using anion exchange resins, oxides of color developing agents, oxides and decomposition products of preservatives, and even nutrients from silver halide color photographic light-sensitive materials are produced. eluates accumulate in the color developer,
It has become clear that this method changes the finishing performance of silver halide color photographic materials, and in particular increases sensitivity fluctuations and increases in fog. Also, another issue is
The problem is that the image storage stability of the color photosensitive material after processing deteriorates, and yellow stain increases especially under storage conditions of high temperature and high humidity. For this reason, it is difficult to continue reusing it for a long period of time, and it is necessary to replace part of the color developer with fresh color developer at regular intervals, or discard part of the used color developer and constantly replenish a certain amount of new developer. In order to reuse the product and compensate for any changes in performance, it required complicated management, such as adjusting the pH and composition of the color developer.

(Problems to be Solved by the Invention) Therefore, the present invention provides a method for repeatedly reusing (hereinafter referred to as regeneration) in a color developing solution using an anion exchanger.
Provides a method for processing silver halide color photographic materials that prevents fluctuations in sensitivity, fog, and poor image storage properties, and enables virtually zero discharge of color developer without complicated management procedures. It's about doing.

(Means for Solving Section @) The present invention provides a silver halide color photographic material to be processed when regenerating a color developing solution using an anion exchanger. This was completed based on the knowledge that the above problems could be solved by containing at least one pyrazoloazole-based magenta coupler in all.

General formula (I) (wherein, R1 represents a hydrogen atom or a substituent group, and X represents a hydrogen atom or all groups that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Za, Zb, and Zc is methine, substituted methine, =N- or -NH-
'i is represented, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond.

When Z b -Z c is a carbon-carbon double bond, it includes the case where it is a part of an aromatic ring. Furthermore, R1 or
This also includes the case where all dimers or more multimers are formed. Matsugu, Z.
When a, Zb or Zc is a substituted methine, the case where the substituted methine forms a multimer of λ-mer or more is also included. ) General formula (I)'e will be explained in detail below.

In the general formula (I), R1 represents a hydrogen atom and each represents a substituent group, and each represents a hydrogen atom and each represents a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Za, Zb and Zc are methine, substituted methine, =N-
or -NH-7, Za-Zb bond and Zb-Zc
One of the bonds is a double bond and the other is a single bond. The case where zb-Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Furthermore, □ also includes the case where #'iX forms a multi-one body of two or more dragon bodies. Also Za,
When Zb or Zc is substituted methine, its fIL
This also includes the case where all multimers larger than a child's body are formed with methine.

In the general formula (I), a multimer means one having one or more groups represented by the general formula (I) in one molecule, and includes bis forms and polymer couplers. Here, the polymer coupler is a monomer having a moiety represented by the general formula CI (preferably one having a vinyl group),
A homopolymer consisting only of vinyl monomer (hereinafter referred to as vinyl monomer) may be used, or a copolymer may be prepared together with a non-color-forming ethylene-like monomer that does not couple with the oxidation product of the aromatic-grade amine developer.

The compound represented by the general formula (I) has a j-membered ring -! It is a membered ring-fused nitrogen heterocyclic coupler, and its color-producing nucleus exhibits isoelectronic aromaticity with naphthalene, and has a chemical structure that is generally referred to as azapentalene. Among the couplers represented by the general formula (I), preferred compounds include /H-imidazo[/, 2-b]pyrazoles, /H-pyrazolo(/,
, t-b) pyrazoles, /H-pyrazolo(t, 1-C
)(/,,2.Hiroshi) Triazoles, /H-pyrazolo(
/, t-b) (/, 2.≠] triazoles, /H-bilane oC1,j-d) torazoles and /H-pyranoO(/+ja)benzimidazoles, each having the general formula (n)(,1tl)(IV)(V)l
) and (■), particularly preferred compounds are (I[), (IV) and (V). A more preferred compound is (V).

(f[) (III) (I'li') (V) General formula (If) ~ (■) t! The substituents R2, R3 and R4 are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic group, acyloxy group, carbamoyloxy group, silyloxy group , sulfonyloxy group,
Acylamino group, anilino group, ureido group, imide group,
Sulfamoylamino group, carbamoylamino group, alkyltheo group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group ,
Alkoxycarbonyl group, aryloxycarbonyl group t-fi, X is a hydrogen atom, a halogen atom, a carboxy group, or a group that bonds to the carbon at the coupling position via an oxygen atom, nitrogen atom, or sulfur atom, and decouples. destroy the foundation.

The case where R2, R3, R4 or X becomes a divalent group and forms a bis body is also included. It's dangerous, general formula (II) ~ (■
) is in the vinyl monomer,
几2, R3 or R4 represents a simple bond or a linking group, through which the moiety represented by formulas (II) to (■) and the vinyl group are bonded.

More specifically, R, 2, R3 and R4 are hydrogen atoms, halogen atoms (e.g. chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, propyl group, i-propyl group, t-butyl group, tri-butyl group, Fluoromethyl group, tridecyl group, j-(2,Hiro-di-t-amylphenoxy)propyl group, codedecyloxyethyl group, 3-phenoxypropyl group, cohequinolsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc.), aryl groups (e.g.
7 x = A/ group, ≠-t-butylphenyl group, 2
．． ≠-di-t-amylphenyl group, ≠-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., caufuryl group, λ-thienyl group, cobyrimidinyl group, copenzoteazolyl group, etc.), cyano group, Alkoxy groups (e.g. ethoxy group, ethoxy group, λ-methoxyethoxy group,
codedecyloxyethoxy group, -monophenoxyethoxy group, λ-methanesulfonylethoxy group, etc.), aryloxy group (e.g., phenoxy group, λ-methylphenoxy group, ≠-1-butylphenoxy group, etc.), Heterocyclic oxy groups (e.g., cobenzimidazolyloxy groups,
), acyloxy groups (e.g., acetoxy, hexadecanoyloxy, etc.), carbamoyloxy groups (e.g., N-phenylcarbamoyloxy, N-ethelcarbamoyloxy, etc.), silyloxy groups (e.g., trimethylsilyloxy), group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), acylamino group (e.g., acetamido group, benzamide group, tetradecanamide group, α-(co.

Hiro-dyl t-amylphenoxy)butyramide group, γ-
(3-t-butyl-≠-hydroxyphenoxy)butyramide group, α-(Hiro-(≠-hydroxyphenylsulfonyl)phenoxy)tecanamide group, etc.), anilino group (e.g., phenylamino group, cochloroanili Z group,
λ-chloroj-tetradecanamidoaniυ) group, Coke 0O-j-dodecyloxycarbonylanilino group, N
・-7 cetylanilino group, cochloroloyo-(α-(3
-1-butyl-≠-hydroxyphenoxy)dodecanamido)anilino group, etc.), ureido group (e.g., phenylureido group, N-butyl-N'-methylureido group,
methylureido group, N, N dibutylureido group, etc.)
, imido group (e.g., N-succinimide group, 3-penzylhydantoynyl group, ≠-(2-ethylhexanoylamino)phthalimide group, etc.), sulfamoylamide Z
groups (e.g., N, N-dipropylsul, 7amino to hemether, monodecylsulfamoylamino, etc.), alkylthio groups (e.g., methylthio, octylthio, tetradecylthio, cophenoxyetherthio) group, 3-phenoxypropylthio group, 3-(l/
L-t-butylphenoxy)propylthio group, etc.), arylthio group (e.g., phenylthio group, copoxyj-1-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, Hiroshi-
tetradecaneamidophenylthio group, etc.), heterocyclic thio group (e.g., 2-benzoteazolylthio group, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryl Oxycarbonylamino group (e.g.
Phenoxycarbonylamide group, 0μm tert
-butyl 7eno dicarbonylamino group, etc.), sulfonamide group (e.g. methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group,
p-) luenesulfonamide group, octadecanesulfonamide group, λ-methyloxyj- to monobutylbenzenesulfonamide group, etc.), carbamoyl group (e.g.,
N-ethelcarbamoyl crystal, N,N-dibutylcarbamoyl group, N-(J-dodecyloxyethyl)carbamoyl group, hemeterhetodecylcarpamoyl i, N-
(J-(ko, Hiro-G-tert-amylphenoxy)
propyl) carbamoyl group, etc.), acyl group (e.g.
acetyl group, (2,≠-di-tert-amylphenoxy)acetyl group, benzoyl group, etc.), sulfamoyl group (e.g., N-ethersulfamoyl group, N,N-dipropylsulfamoyl group, N-(2 -dodecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N,N-diethylsulfamoyl group, etc.), sulfonyl group (e.g., methanesulfonyl group,
octane sulfonyl group, benzenesulfonyl group, toluenesulfonyl fi, etc.), sulfinyl group CH, octane sulfinyl group, dodecyl sulfinyl group, pheni, rusulfinyl N, 'f? ) s alkoxycarbonyl group (e.g., methoxycarbonyl group, bunaloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, 3-pentadecyloxycarbonyl group) , etc.); group, benzoyloxy group, co, ≠-dichlorobenzoyloxy group, ethoxyoxaroyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, Hiro-cyanophenoxy group, ≠-methanesulfonamide phenoxy group, Hiro- Methanesulfonylphenoxy group, α-7toxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, cocyanoethoxy group, benzyloxy group, 2-7eneteloxy group, cophenoxyethoxy group,! -phenyltetrazolyloxy group, λ-benzothiazolyloxy group, etc.), groups linked through nitrogen atoms (e.g. benzenesulfonamide group, N-
Ethyltoluenesulfonamide group, heptafluorobutanamide group, 2.

3, lA,! , 1s-pentafluorobenzamide group,
λ, 3. Hiro! , 6-bentafluoropenzamide group,
Octanesulfonamide group, p-cyanophenylureido group, N,N-diethylsulfamoylamino group, /-
Pi is a lysyl group! ,! -dimethyl-2. goodioxo
3-oxazolidinyl group, /-benzyl-ethoxy-3
-hydantoinyl group, -N-/,/-dioxo-J(,
2H)-oxo-/, 2-benzisothiazolyl group, co-oxo 1. Kodihyde O-/-pyridinyl group, imidazolyl group, pyrazolyl group, 3. ! -diethyl/,,
2.4'-triazol-l-yl group, j-order is 6
-benzotriazol-l-yl,! -Methyl-1. Ko, 3. ≠-triazole-/-(ru group, benzimidazolyl group, 3-benzyl-7-hydantoinyl group, /-benzyl-!-hexadecyloxy-3-hydantoinyl group, !-methyl-7-tetrazolyl group, ≠-
methoxyphenylazo group, ≠-pivaloylaminophenylazo group, cohydroxy-Hiro-probanoylphenylazo group, etc.), groups linked by a sulfur atom (e.g., evaporation, phenylthio group, λ-carboxyphenylthio group, copoxy j-1-octylphenylthio group, ≠-methanesulfonamidophenylthio group, 2,3-dibutoxyphenylthio group, ≠-methanesulfonylphenylthio group, Hiro-octanesulfonamidophenylthio group, copetoxyphenylthio group , ≠-dodecyloxyphenylthio group, 2-(,2-hexanesulfonylethyl)-t-te
rt-octylphenylthio group, benzylthio group, cocyanoetherthio group, l-ethoxycarbonyltridecylthio group,! -Phenylluco.

3,≠,! -tetrazolylthio group, -1penzothiazolylthio group, -1dodecylthio group, codedecylthio-!
-thiophenylthio group, cophenyl-3-dodecyl-
/, 2. 1/L-triazolyl-yo-thio group, etc.).

When R2, R3, R4 or X becomes a divalent group to form a bis body, this divalent group is described in more detail as follows:
Substituted or unsubstituted alkylene groups (e.g., methylene group, ethylene group, /, 10-decylene group, -CH2CH2
-0-CH2CH2-, etc.), a substituted or unsubstituted phenylene group (represented by R2, R3 or R4 when present in the monomer, /, 4L-phenylene group, /, 3-phenylene group, The linking group is an alkylene group (substituted or unsubstituted alkylene group, for example, methylene group, ethylene group, /, 10-decylene group, -CH2CH20CH
2C) 12-1 etc.), phenylene group (substituted or unsubstituted phenylene group, e.g. l, Hiro-) unicine group, /
,! -phenylene group, -NHCO--CONH--0--0CO- and aralkylene group (for example, -NHCO-2-CON of CH3) l- group (R2 is a substituted or unsubstituted alkylene group, and is a phenylene group) represents.

What is represented by general formulas (If) to (■) is building α etc.).

In addition, the vinyl group in the vinyl monomer has the general formula (II)
It also includes cases where it has substituents other than those represented by ~(■). Preferred substituents are hydrogen atoms, chlorine atoms, and lower alkyl groups having 1 to .mu. carbon atoms.

Acrylic acid, α
- Chloroacrylic acid, α-alacrylic acid (e.g., methacrylic acid, etc.) and esters or amides derived from these acrylic acids (e.g., acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide) , methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-
ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-human Ooxy methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate),
acryloni, tolyl, methacrylate tolyl, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid,
S-water maleic acid, maleic ester, N-vinyl-!
-pyOlidone, N-vinylpyridine, and 2- and ≠-vinylpyridine. It also includes the case where two or more of the non-chromogenic ethene-like unsaturated monomers used herein are used in combination.

Compound examples and synthesis methods of couplers represented by the general formulas (I[) to (■) above are described in the documents listed below.

The compound of general formula (II) is disclosed in JP-A-Sho! Tar76λ! ≠ etc., the compound of general formula (III) is
Otsu! In the 2nd class, the compound of general formula (■) is
7≠//, etc., the compound of general formula (V) is JP-A-Shojter/7/ri! 6 and 60-/72 t2, etc., the compound of general formula (■) is disclosed in JP-A-60-33! In addition, the compound of general formula (■) is described in US Patent No. 3.06/, Kou No. 32, etc., respectively.

Also, -1-IA20'A in Tokkai Sho! , 1m! ? −
2/+rztt, 39-17m3, +fJ! F-/7
7! Kugu and the same! Tar/77! The highly color-forming Palast group described in J-7 etc. has the above general formula (II) to (
■) Applies to any of the compounds listed above.

Specific examples of the pyrazoloazole coupler used in the present invention are shown below, but the invention is not limited thereto.

(M-/) (M-, ri (M (M-da) CM-j) (M-4) (M-/J) (M-/4/-) (M-/j) ii3n-cisF113 (M-t6) (M-77) n-C4H* (8 (-X3) (M-ko) CH.

(M-Ji (M-27) (M-2, r) (M-Jr) (M-32) (M-≠0) amount CH3 (M-ttti) (M-≠2) CH.

(M-μri) (M-jθ) (M-!ko) (M-Evening 6) 8t'1171tl I-l- 1s(&O) H3 (M-J-7) (M-jr) CH.

\ OH1 (M-7!1/) (M-1, 2) 06H13(tl (M-Bu3) (M-6≠) (M-lI7) (M-AI) x:y=jO:! 0 (Weight ratio, same below) x:y=μ0:60 x: y=zo: j.

(M-&j) x : y=! 0:! r0 (M-1&)
i/X/0-2MotbNaIl,jX/0-1
molar added.

For the above couplers, etc., in order to satisfy the characteristics required for photosensitive materials, 2a1 or higher types can be used together in the same layer, or the same compound can be added to different 7'C, 2r@ or higher. , of course it doesn't matter.

In order to introduce the coupler into the silver halide emulsion layer, known methods such as those described in US Pat. No. λ,32,027 can be used. For example, phthalic acid alkyl esters (dibutyl 7-talate, dioctyl phthalate, etc.),
Phosphate esters (diphenyl phosphate, triphenyl heptophosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (
(e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethersuccinate, diethyl azelate), trimesic acid esters (e.g. trimesic acid lower alkyl acetyl acetate such as ethyl acetate, butyl acetate, ethyl pionate, λ-class Budel alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, It is dissolved in methyl cellosolve acetate, etc., and then dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Next, a method for regenerating a nine-color developer using an anion exchanger according to the present invention will be described.

The present invention is applied to a method in which the entire processing of a silver halide color photographic material is carried out continuously while adding a replenisher KTLS to a color developing solution.

The procedure for this reproduction is as follows.

Used color developer → 7 = +7 n&eΣNm → erase " - complement ・p supplement → Color developer replenisher, that is, the used color developer is subjected to the above treatment and reused as a replenisher. Used Usually, the color developing solution is recovered and used after overflowing from the color developing tank by supplying a replenisher.

Although various anion exchange resins can be used as the anion exchanger, it is preferable to use a strongly basic anion exchange resin having a quaternary ammonium salt type exchange fund because of its particularly large exchange capacity for halogen ions. These anion exchange resins are based on a styrene-divinylbenzene copolymer, and especially have a divinylbenzene content of 3 to 7.
．． Two pieces are preferred. The quaternary ammonia salt type exchange group will be further explained.

The basic structure 2 of anion exchange resin is shown below.

X=Counter ion R1, R2, R3 is preferably an alkyl group having 7 to 7 g of carbon atoms, and specifically, R1.

Examples include ammonium, trihexylammonium, and trimethylammonium types. Among these, trimethylammonium type resin is preferred because it is easily available as a commercial product, and examples of products include O
- Amberlite IRA manufactured by Mu & Haas - ≠ 0
0. I-A-Hiro 10, Revateit Mlp manufactured by Bayer
00. Diaion 5A-IOIL manufactured by Mitsubishi Chemical Corporation,
FA-4L/I etc'! ! -I can give.

The counter ion of an ion exchange group can be converted into various types by contacting with a solution of the salt of the ion, but it exchanges with the halogen ion in the color developing solution and elutes into the solution, which affects processing performance. It is necessary that the ion does not affect
From this point of view, specific examples include carbonate ions, bicarbonate ions, hydroxide ions, sulfate ions, nitrate ions, phosphate ions, hydrogen phosphate ions, oxalate ions, etc., but they are easy to exchange with halogen ions. Carbonate ions, bicarbonate ions, hydroxide ions, and phosphate ions are particularly preferred because they are commonly used in color developing solutions and have the effect of replenishing components by being eluted.

To retain these counterions, 0.1N to 1It
Contact the resin with a solution of sodium carbonate at a degree of N, potassium on charcoal, sodium on charcoal, potassium bicarbonate, sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate solution.

Any method may be used to bring the anion exchange resin containing counterions into contact with the used color developing solution, but from the viewpoint of ease of operation and efficiency of ion exchange, it is preferable to use the resin. A preferred method is to pass a color developing solution through a packed column and bring them into continuous contact. In this case, the flow rate of the color developing solution is set to increase the efficiency of the ion exchange reaction.
The amount is preferably in the range of 0.3 to io times the volume of the resin layer in 7 hours, particularly Q, 3 to 3 times, and more preferably O0! ~3 times is preferred. After processing with an anion exchange resin, the color developing solution is supplemented with the corresponding component in order to compensate for the consumption of the component due to processing and the decrease in component due to adsorption to the anion exchange resin.

The nature of the components to be supplemented can be confirmed by chemical analytical means.

Ingredients that normally need to be supplemented include color developing agents, preservatives such as sulfite hydroxylamines, and if necessary, chelating agents, buffers such as carbonates, phosphates, potassium hydroxide, sodium hydroxide, etc. agent, alkaline agent t-supplement.

The color developing replenisher prepared after replenishing these components contains each component at a higher concentration than the concentration that should be maintained in the color developing tank, and the concentration ratio of the replenisher to that in the color developing tank is is usually l.

It is 0-2.0. This ratio varies depending on the set replenishment amount, and increases as the total replenishment amount is reduced.

When the replenishment amount is 1004 or more per photosensitive material, the ratio is preferably in the range /, 0-/, j'. The same applies to the pH, and the pH within the color developing tank is 0. ／〜／
, 0 is normally set to a high value, and the relationship with the replenishment amount is also the same as above.

In the recycling process carried out in the present invention, when the color developing solution is replenished tVi photosensitive material is a color print material, joat ~ JOO per m'' of the photosensitive material.
t, preferably 100xt~2! Od.

The most preferred is /30d-hereθd. Also, in the case of photographic materials such as color negative film and color reversal film, itr? per 300-3000m, preferably ≠oo-izoow, most preferably ≠00-
/200d. The larger the amount of replenishment, the easier it is to stabilize the performance, but to avoid conversely increasing the frequency of regeneration processing, the above-mentioned preferred range is set as an appropriate range for the balance between the two.

Journal of Applied Photographic Engineering Vol. The effect of the present invention is that the provision of a contact treatment step between the adsorbent and the color developing solution described in Volume 7g6 Hiromu (Autumn issue of 1999), pages 2/6 to 21, page 1, reduces sensitivity fluctuations. This is a preferred embodiment because it further increases the .

Fi% Kaisho as an adsorbent that can be used in the present invention! 3-/,
In addition to the phenol-formaldehyde-type adsorbent resin, activated carbon, and surface-modified activated carbon described in No. 3234t3, Diaion Manual (II) published by Mitsubishi Chemical Corporation (/P
♂! The polystyrene type adsorptive resin gold described on pages 2 and 6 of Hirobaji (2007, edition) can be mentioned.

In the present invention, the anion exchange resin whose exchange capacity has decreased is recycled. The regeneration treatment of the anion exchange resin can be carried out by a known method, for example, the Diaion Manual (I) published by Mitsubishi Kasei Corporation iJ■
4) / F page-, 2/ The operating method described on page 2/ is mentioned.

The liquid used for regenerating the anion exchange resin can be the same as that used for retaining the preferred counter ions described above.

However, in order to increase the regeneration efficiency, for example, a sodium chloride solution is used to elute the iodine ions and bromine ions that are collected on the resin, and then a solution of sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, etc. is used to elute the preferred counter ions. It is also possible to carry out processing for exchanging it.

Through the process described above, the accumulated halogen ions in the color developer are removed and the developing activity is restored by replenishing the consumable components, but only the anions are sufficiently removed in the above process, and the oxidation of the color developer oxidants and decomposition products of preservatives such as hydroxylamine or chelating agents such as amino/polyphosphonic acids and aminopolycarboxylic acids, anti-irradiation dyes eluted from silver halide color photographic materials, and color enhancers. A wide variety of components, such as sensitive dyes, surfactants, and antifoggants, are not removed or are only removed unreliably, and accumulate in the color developing solution each time the regeneration is repeated. Moreover, the accumulation of these components varies depending on the degree of fatigue of the anion exchange resin, the flow rate of the color developing solution, the method of regenerating the anion exchange resin, and the presence or absence of adsorbents in the previous process. This affects the sensitivity of the magenta coloring layer, changes in the fog density of the magenta dye, and increases in yellow stain when stored under high temperature and high humidity conditions.

The present inventors have found that by selecting a specific 7-zenta coupler represented by the general formula (I), the influence of such complex accumulations on color photosensitive materials can be greatly reduced, and color development can be improved. The present invention was completed after discovering the unexpected effect that the developer can be completely reused semi-permanently.

Although there is a large amount of accumulated substances in the regenerated color developing solution of the present invention, it is characterized in that the accumulation of halogen ions is small, unlike a low replenishment process in which the amount of replenishment is simply reduced.

The present invention is effective when the concentration of halogen ions in the color developing solution is below a certain level, and 2
x10"mol/A or less, especially 8j X/0-
2 mol/i or less, more preferably /, 2 x 10-2 mol/L or less, and 4Lxio-2 mol/L or less for chlorine ions, especially n
3xio”-3 morphs 1 or less, or even 1, 7X10
It is preferable if it is less than mol/L.

Next, the color developing solution used in the present invention will be explained.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is p-
It is a phenylenediamine derivative, and representative examples are shown below, but the invention is not limited to these.

D-/N, N-diethyl-p-phenylenediamine D-co-co-amino-diethylaminotoluene D-32-amino-β-(N-dithyl-hera-valylamino)-toluene D-≠ μ-[he-ether-N-( β-hydroxyethyl)aminocoaniline D-7comethyl-≠-[h-ethyl-N-(β-hydroxyethyl)aminocoaniline D-A 4t-amino-3-methyl-N-ethyl-to-[β-(methanesulfone) amido)ethylcouaniline D-7N-(2-7minor!-diethylaminophenylethyl)methanesulfonamide D-r N,N-dimethyl-p-phenylenediamine D-2-rest-amino-3-methylheetherhe Methoxyethelaniline D -10≠-amino-3-methyl-heether-he β-ethoxyethylaniline D -// 4L-amino-3-methyl-he-ether-he β-butoxyethylaniline above p-7 Among the amine rust conductors, especially color-forming,
Stability of the dye formed, stability of the compound itself, handling i
From the above safety point of view, D-4 and D-j are preferable, especially D-
4 is preferred.

Moreover, these p-7 unilene diamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and ly-)luenesulfonates. The amount of the aromatic-grade amine developing agent used is developer/1. Good luck n/? -201, which is a better concentration of 3y to 10ji.

In addition, the color developer contains sodium sulfite and preservatives.
Sulfites such as potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl t(ffl acid adducts) can be added as necessary.

The preferred addition amount is color developer/L Sushiri O0! y～lQ
F more preferably /y-! It is.

In addition, as a compound that directly collects the color developing agent,
Hydroxylamine, WO♂710'AjJ44 No. 7
Dialkylhytomyxylamine (diethylhydroxylamine in %) described on page to page t JP-A-1S3
-/7064c2 hydrazide y (specific example 1 in %)
-// compound), same 63-1 bow! No. 6 and No. 63-J
-rμ≠Phenols described in No. 3, No. 63-≠1A4j
It is preferable to add α-hydroxyketones and α-7 minoketones described in No. A and/or various types described in No. Aj-j121A≠. Also, when used in combination with the above compounds, WO♂710≠! It is particularly preferable to add the fluoramine (triethanolamine in %) described in No. 3≠No. 13 B-1 to No. 1≠I-G from the viewpoint of improving storage stability.

Other fecal collection agents include JP-A-77-4'! /L/≠ and food metals described in 7-637≠, salicylic acids described in JP-A No. 3 μm 3332, salicylic acids described in JP-A No. 3 μm 3332. Polyethyleneimines described in JP-A No. 6-ta-4t3, U.S. Pat. No. 3.7-6. ! The aromatic polyhydroxide compounds described in ≠≠ may be included as necessary. In particular, aromatic polyhydroxy compounds are highly effective in inhibiting deterioration of developing agents and hydroxylamine due to the oxidation catalytic action of metal ions, and are therefore preferred for use in the present invention.

The color developing solution used in the present invention preferably has a pH of
/, 2, more preferably,! ~//, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, 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, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, O-
Sodium human mixibenzoate (sodium salicylate), potassium 0-hydroxybenzoate,! -Thulho λ
-Sodium hydroxybenzoate (!-Sodium sulfosalicylate),! Potassium -sulfo-2-human a-xybenzoate (potassium sulfosalicylate) and the like can be mentioned. However, the present invention is not limited to these compounds.

Addition of the buffer to the color developer solution, 0.1 mol/
It is preferably 2 or more, especially 0.1 mol/! ~O
, 4tmo/i is particularly preferred.

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.

As the chelating agent, organic acid compounds are preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.

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

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N'N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, /, 2- diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid,
Etheno/diamine orthohydroxyphenylacetic acid, λ-
Phosphonobutane/2. ≠-Tricarfonic acid, /-hydroxyethylidene-/, /-diphosphonic acid, N, N'
-Bis(cohydroxybenzyl)ethylenediamine-
N,N'-diacetic acid and these chelating agents may be used in combination if necessary.

Among the above chelating agents, it is not captured by the anion exchange resin during the developer regeneration process, functions stably even during long-term regeneration use, and has a high fecal collection effect on the developing agent, hydroxylamine, and dialkylhydroxylamine. In particular, l-hydroxyethylidene-/,/-diphosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N,N,N-trimethylenephosphonic acid Acids are preferred. Addition of these chelating agents MJi
It is sufficient that k is a shield sufficient to completely sequester calcium, magnesium, and other metal ions in the one-color developer.

Normal color developer/per liter/X10-3 mol~/X/
0"-" moles, preferably 3X/0-3 moles-3X1()2 moles.

If necessary, an antifoggant can be added to the color developing solution of the present invention. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, and! - Nitroinindazole! -Methylbenzotriazole, j-nitrobenzotriazole,! Examples include nitrogen-containing heterocyclic compounds such as lyrubenzotriazole, λ-thiazo, lyrubenzimidazole, cortiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developing solution used in the present invention may contain a fluorescent whitening agent. As an optical brightener, ≠.

μ'-diami/-2,2'-disulfostilbene compounds are preferred. Separately placed FiO-J″P/ is preferably o
, iy-HiroP/i.

Furthermore, various surfactants such as alkylsulfonic acid, ary-phosphonic acid, aliphatic carmenic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature of the color developing solution of the present invention is 20-JQC, preferably 30-60C. Processing time is 20 seconds! It is set in the range of 30 seconds to 7 minutes, but in the processing of high-silver chloride color light-sensitive materials with a silver chloride content of JM or more, a time of 30 seconds to 7 minutes is particularly preferable. , 1 minute to 3 minutes 30 minutes for silver iodobromide color light-sensitive materials
Seconds are preferred.

Further, the developing bath may be divided into three baths or more as necessary, and the color developing replenisher may be replenished from the first bath or the last bath to shorten the developing time and reduce the amount of replenishment.

The processing method of the present invention can also be used for color reversal processing. In the present invention, the black-and-white developer used at this time can be a so-called black-and-white first developer used in the reversal processing of color photographic light-sensitive materials, which is commonly known, or a developer used in the processing of black-and-white light-sensitive materials. Additionally, various well-known additives commonly added to black and white developers can be included.

Typical additives include l-phenyl-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Examples include inorganic or organic inhibitors such as potassium bromide, comethylbenzimidazole, and methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. be able to.

In addition, it is more preferable that be/zyl alcohol, which is widely used as a color development accelerator in the practice of the present invention, is not contained. Benzyl alcohol physically adsorbs on anion exchange resin and has the effect of reducing the ion exchange reaction rate. Therefore, in order to reliably collect the halogen ions in the color developing solution and maintain stable processing performance, it is preferable not to use benzyl alcohol, and high chloride color photographic sensitizers that allow sufficient color development without using benzyl alcohol. The invention is particularly preferred for application to materials.

Next, the steps subsequent to color development will be explained.

The silver halide color photographic light-sensitive material after color development can be processed by the steps described below.

1. Color development - Bleach fixing - Water washing (stable) 2. Color development -
Washing with water (stop) - bleach fixing - washing with water (stable) 3. Color development - constant bleaching, washing with water (stable), drying Color development - washing with water (stop) - constant bleaching, washing with water (stable)! 0 color development - washing with water (stop) - bleaching - washing with water (stable) constant fixation - washing with water (stable) In the above, the numbers in parentheses indicate alternative steps.

First, the bleach-fix solution will be explained.

As the bleaching agent used in the bleach-fix solution, organic acid ferric complex salts such as aminopolycarboxylic acid and ami/polyphosphonic acid are used, and specific examples include ethylenediaminetetraacetic acid,
Examples include ferric complex salts of diethylenetriaminepentaacetic acid and cyclohexanediaminetetraacetic acid.

The amount of these bleaches to be used is 0.000.
02 to O0j mol, and O1/-0# mol is particularly preferred from the viewpoint of desilvering properties, cyan dye recoloring properties, and stain prevention. When using the above-mentioned organic iron ferric complex salt, it is usual to add a free organic acid in a molar ratio of about 1/10.

As the fixing agent, known fixing agents such as ammonium thiosulfate and sodium thiosulfate are used. In addition, sulfites such as sodium sulfite and ammonium sulfite are used as preservatives, but aromatic sulfinic acids such as benzenesulfinic acid and para-toluenesulfinic acid can also be used in combination with these or as a substitute for preservatives. Preferable in terms of sex and gender.

Furthermore, bleach accelerators described in JP-A-62-2222J2 and bromides such as ammonium bromide can also be used.

pHFi3~ of bleach-fix solution! The preferred pH is ≠, from the viewpoint of promoting desilvering, improving color restoration, and preventing staining. - It's Q, especially! , O~7. !
It is. Temperature box for bleach-fixing process! ~≠! The temperature is preferably 30-≠0°C, particularly preferably 33 to 31r''C, from the viewpoint of rapidity and maintenance of stability.

The bleach-fix solution may be separated into two steps: bleaching and fixing. The separation process of bleaching and fixing is described in the technical data published by Agfa Gewald <1 yr. It can be implemented in combination with

The bleaching solution includes the bleaching agent described for the bleach-fixing solution,
The bleach accelerator ammonium bromide is likewise used, and other compounds known as metal corrosion inhibitors such as ammonium nitrate may be added. The pH of the bleaching solution is 3.0-r, 0. Preferably μ, O~7°0% KtE or μ,! ~6.
j, and this range provides the best balance between desilvering properties and cyan dye recoloring properties.

As for the fixing solution, those described above regarding the fixing components of the bleach-fixing solution can be used. pH of fixer,
o-a', o, preferably t, o~7°j.

For other information on bleaching solutions, bleach-fixing solutions, and fixing solutions, see JP-A No. 3-i≠≠3jJ, page λt, lower left column ~ 3o-<
- Bleach solution and bleach-fix solution in the lower right column.

All statements regarding fixer fluids are applicable.

In addition, the bleach-fixing time is 30 seconds to λ minutes, and the bleaching time is 30 seconds to λ minutes.
2 minutes, the fixing time can be set in the range of 30 seconds to 1 minute and 30 seconds, and the bleach-fixing and bleaching times can be set short by lowering the pk4' of the solution.

The amount of replenishment of bleach, bleach-fix solution, and fixing solution depends on the color-sensitive material/lr/container. It can be set in the range of 330 to 300 tl, and the preferable range is jO-2!0IIj in view of the balance between ensuring quality such as desilvering performance and reducing emissions. In addition, all of these processing solutions can be recycled and reused using known methods. 6-33627, method for supplementing insufficient components in overflow, JP-B No. 67-/
The method using the electrolytic silver recovery device described in No. 63≠j can be applied.

Next, the washing with water or stopping step after color development and damage will be explained.

These steps are intended to facilitate the regeneration and to prevent the color developing solution from being brought in when the solution in the next step is recycled. is used.

A typical acetic acid stop solution is glacial acetic acid/water solution.

The processing method of the present invention is comprised of processing steps such as secondary 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 can contain known additives, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
Disinfectants and fungicides (for example, intiazolone, organochlorine disinfectants, benzotriazole, etc.) that prevent the growth of various bacteria and algae, surfactants that prevent drying load and unevenness, and the like can be used. Mano is L, E.

West, “Water Quality Cr1te
ria”Photo, 8ci, and Eng.
vol,ri,AA.

page34g 4L~3! ? (/ri6yo) etc. can also be used.

As the stabilizing liquid used in the stabilizing step, a processing liquid that can stabilize a dye image is used. For example, a solution having a buffering capacity of pH 3 to 6, a solution containing an aldehyde (for example, formalin), etc. can be used. The stabilizing liquid may contain ammonium compounds, metal compounds such as Bi and Ai, optical brighteners, chelating agents (e.g. /-hydroxyetherithene-/, /-diphosphone eR), bactericides, fungicides, A hardening agent, a surfactant, etc. can be used.

In addition, the water washing step and the stabilization step are preferably carried out by a multi-stage countercurrent system, and the number of stages is preferably from λ to ≠ stages. The supplementary charge is 7 to 10 times, preferably 2 to 30 times, and more preferably 2 to 75 times the amount brought in from the prebath per unit area.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
, water that has been deionized to have Mg 9 degrees below 3197ft,
It is preferable to use water that has been sterilized with a halogen or ultraviolet germicidal lamp.

In each of the above processing steps for photosensitive materials, when continuous processing is performed using an automatic processing machine, 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. To compensate for such concentration of the processing solution, it is preferable to replenish an appropriate amount of water or correction solution.

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.

In addition, all the descriptions regarding water washing and stabilizing solution in the lower right column to lower left column of JP-A-63-/Hiro 4L3 j'3, page 30 can be applied.

Next, the silver halide color photographic material used in the present invention will be described.

The present invention can be applied to various photosensitive materials such as color paper, color reversal paper, color negative film, color reversal film, color autopositive paper, etc., but it is most preferably applied to color paper.

The silver halide emulsion of the light-sensitive material processed by the method of the present invention contains at least seven or more of silver chloride, silver bromide, and silver iodide, but in the case of color paper, it does not substantially contain silver iodide. Silver chlorobromide is preferred. Substantially no silver iodide means that the content of silver iodide relative to the total amount of silver halide is 1 mole or less, preferably 0.3 mole or less, and more preferably 0.7 mole or less. Most preferably, it contains no silver iodide at all.

The color - and e- emulsions preferably used in the present invention are silver chlorobromide emulsions having a silver bromide content of 10 moles or more. In particular, in order to obtain an emulsion having a sufficient l&lpar; degree without increasing fog, it is preferable that the silver bromide content is 20 molti or more. However, when rapid processing with shortened development time is required, a silver chlorobromide emulsion with a silver bromide content of 70% mol or less is preferred, and a silver chlorobromide emulsion with a silver bromide content of 3 mol or less is particularly preferred. Preferably, silver chloride emulsions containing substantially no silver bromide and having a silver bromide content of 1 molt or less are more preferable.

Reducing the silver bromide content (gold) not only improves the development speed, but also reduces the development g
Since the number of bromide ions eluted into the l solution is reduced, developing activity can be maintained with a smaller amount of replenisher.

The halogenated mackerel grains in photographic emulsions may be so-called regular grains having regular crystals such as cubes, octahedrons, dodecahedrons, and polydodecahedrons, or may have irregular crystal shapes such as spherical shapes. It may have crystal defects such as twin planes, or a composite form of these.

The grain size of the silver halide may be fine grains of about 0.001 microns or less, or large grains with a projected area diameter of about 10 microns, and may be monodisperse emulsions with a narrow distribution or polydisperse emulsions with a fairly wide distribution. So 4 good.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, as described in Research Disclosure (
RD), A6/76 Hiro J (/ri7 December 2013), 2.2
~23 pages, @1. Emulsion pre
paration and types)' and same, /16/171tC/179/July), t4tr
You can follow the method described on page.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chimie et Phys
iquePbotographique Paul M
ontel, /9lI7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F,
Duffin, PhotographicEmu
lsion Chemistry (Focal Pr.
ess15'Ai, "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Vol.
an et al, Making and Coat
ingPhotographic Emulsion
, Focal Press.

It can be prepared using the method described in 64L).

It is preferable to use a monodisperse emulsion in the present invention.

As a monodisperse emulsion, silver halide grains having an average grain diameter of greater than about 0.1 micron, at least about 3.
Emulsions in which the weight percent is within ±4L0% of the average grain diameter are typical. The average particle diameter is approximately 0. ．． 2j-, 2 microns, with at least about j weight percent or ii quantity of at least about at least about
Emulsions such as those within the 20% range can be used in the present invention.

Tabular grains having aspect ratios of about 3 or greater can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
CE and Engineering), Vol. 111, pp. 2!1r-277 Cl970): U.S. Pat.

1A31A, No. 226, same≠, Hirol≠, No. 31O, same≠
, ≠33.0≠g, same≠, ≠32. ! CoO and British Patent No. 2. It can be easily prepared by the method described in, for example, No. //2.167. The use of tabular grains has advantages such as improved color sensitization efficiency by sensitizing dyes, improved graininess, and increased sharpness, as disclosed in the above-cited U.S. Pat.

It is described in detail in μjIIL, No. 2, etc.

The crystal structure may be --like, or the inside and outside may have different compositions. A typical example of a heterogeneous composition is a core-shell type or double structure type particle in which the interior and surface layers of the particle have different halogen compositions. In such particles, the shape of the core and the shape of the holes in the shell may be the same or different.

Specifically, the core is cubic, the shell is cubic, and the shape of the secondary particle is octahedral, and vice versa. Further, instead of a simple double structure, a triple structure or a more multiple structure may be used, or a core-shell double structure grain may have a thin layer of silver halide having a different composition applied to its surface.

In the light-sensitive material processed by the method of the present invention, it is preferable to use an emulsion consisting of grains having some structure rather than one having a uniform halogen composition within the grains. In filled silver emulsions such as those used in Colorbeno RJt', grains having a halogen composition with a lower silver bromide content on the grain surface than on the grain interior are more preferably used. It is a core-shell type emulsion containing a higher silver bromide content.The difference in silver bromide content between the core and shell parts is more than 3 molar.
It is preferable that the silver content ratio (molar ratio) between the core and the shell is less than molar mass. ~Rij:! More preferably, the ratio is 7:3 to 0:10.

In addition, in a silver iodobromide emulsion such as a color negative film, the core part has a higher silver iodide content than the shell part, and the silver iodide content "4" is 100 moltyl! molt, and even /
Preferably, the shell part contains less than !molar amount of silver iodide, especially less than λ mol amount.The silver content ratio of the core and shell is /!:lr!~za1:
/ 1. Furthermore, /! :r! ~7! :, 2! is preferred.

Such emulsion grains are described in British Patent No. 1,027゜l≠6, US Patent No. 3. ! 0! , 0lslr issue, same≠, ≠μ≠
, T77 and Japanese Patent Application No. 3G-2≠R Kotata.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with meden dyes or the like. Dyes that can be used include cyanine dyes, merocyanine 8-strands, complex cyanine dyes, complex merocyanine dyes, pho-polar cyanine dyes, hemicyanine dyes, steryl dyes, and hemiosol/pol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanif dyes, and complex merocyanine dyes.

The sensitizing dye used in the present invention is f(, E8EA
RCHDI8CL (JSU 几E/7A volume, Item 17
Examples include those described in p.

Here, the sensitizing dye can be used by being present in any step of the manufacturing process of the photographic emulsion, or the sensitizing dye can be used by being present at any stage of the manufacturing process of the photographic emulsion.
It can exist at any stage up to. Examples of the former include a silver halide grain formation process, a physical ripening process, and a chemical ripening process.

In particular, U.S. Pat.
No. 22j, l, No. 66, by adding a spectral sensitizing dye to the emulsion after the formation of stable nuclei for silver halide grain formation, it is possible to increase the photographic sensitivity and prevent the adsorption of the spectral sensitizing dye by the silver halide grains. It is disclosed that there are advantages such as strengthening.

The silver halide photographic emulsion used in the present invention contains the following ingredients for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or stabilizing photographic performance.
Various compounds can be included. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles,
Nitrobenzotriazoles, mercaptothiazoles (%/-phenyl-mercaptotetrazole), etc.; mercazotovirimidis; mercaptotriazines: e.g. oxatri/thione deoketo compounds niazaindenes, e.g. triazaines denes, tetraazaindenes (especially ≠-human axy-substituted (83.3n,
~7) Tetraazaindenes), pentaazaindenes, etc.; many compounds * known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. are added. be able to.

Regarding these, please refer to the Research Disk a-Jar (RD).
)/I6/7! ;44J and 4/J'7/AK 16
c), and all the places mentioned are listed on the clothing below.

/, chemical sensitizer 18 sensitivity increasing agent 3, spectral sensitizer, super sensitizer cap whitening agent! , antifoggants and stabilizers 6, light absorbers, filter dyes UV absorbers 7, stain inhibitors ♂6 dye image stabilizers, hardeners IQ, binders//, plasticizers, lubricants/2. Coating aid, surfactant 13, static inhibitor 23 page 23 ~ λ≠ page λφ 2 ≠ ~ co! Page 2.33-21p Page 23 Right side 2! Page 26 Page 26 Sada 27 Pages 26-27 Sada, 27 pages t4Lr Page right side Same as above 6μ Negative right column ~ 61A Negative right column 64t Negative right column 6 Hiro Negative right column troJT Left to right column 6μ Page 1 left column Same as above 6 Ta Q Sada right column Same as above Same as above Halogenated trowel color processed by the present invention /! ! The Il1 base material can contain various color couplers. For example, Research Disclosure 127/
Typical examples include the cyan, magenta, and yellow dye-forming couplers described in the patents cited in 117/7, February 2013 and 117/7, February 2013. These couplers are preferably made diffusion resistant by introducing a ballast group or by multimerizing two or more molecules, and may be a polymeric coupler or a lambda equivalent coupler. Couplers that diffuse to improve graininess, and DIR couplers that release current-ray suppressants during the coupling reaction and produce edge effects or multilayer effects, can also be used.In addition, couplers that improve graininess by diffusion can also be used. In conjunction with the ring reaction, a group that has the effect of accelerating development or a group that has the effect of fogging silver halide is released, for example, JP-A-Showy-
irot≠! No. 32, same! Tah/!
No. 7631, same! Tar/70ttio issue and special request!
! Compounds described in -11AtO No. 7 and the like can also be used.

Further, as a color coupler, the effect of the compound of the present invention is more likely to be obtained if the ratio of the reference equivalent coupler used is low. Specifically, the proportion of high-equivalent couplers among all the couplers contained in the photosensitive material is! It is preferably less than O mol, more preferably less than Hiro O mol, particularly preferably 30 mol or less.

The yellow coupler is preferably an α-pivaloyl or α-benzoylacetanilide coupler that splits off at an oxygen atom or a nitrogen atom.

Particularly preferred examples of these j-equivalent couplers include:
U.S. Patent No. 3, 'IC#,/5'4', U.S. Pat. 33.301 and US Pat. No. 11.02.2.620, etc., or the oxygen atom separation type yellow couplers described in US Pat. No. 3.273. RTR No., Hiromu No. 3, Hiromu.

No. 023, Tokuko Akira! No. ♂-1073, Tokukai ShojO-/
No. 32ri 2, West German Application Publication No. 2, 2/ri.

No. 17, No. 2.2t/, No. 31sI, No. 2゜3
29.617 and No. 2.1A33.112, etc. ・Others 1. Treatments that are preferably used in the present invention because they have little effect on photographic performance. Liquid components and light-sensitive material components To be more specific, the fluorescent whitening agent of general formula (I) of JP-A No. 63-204t2!7, JP-A No. 63-204t2!7; 22 ≠ No. 36 Yellow coupler of general formula (I) Magenta coupler of general formula (II) Cyan coupler of general formula (IV), (V) If) sensitizing dye, 63-≠! ! No. 60 general formula (Al-/) ~ (
Preferable examples include anti-irradiation dyes such as AI-If/). These couplers, etc.
Particularly preferred are those used in Examples.

As the cyan coupler, a coupler that is robust against humidity and temperature is preferably used. Typical examples include the phenolic coupler described in U.S. Pat. No. 3.772.002; No. 53, special request by Akihiro J.
t-≠267/issue and JP-A-1-13.32-3
Ko,j-diacylamino 7e/
A coupler having a phenylwaleido group at the co-position as described in U.S. Pat. No. 333, Tatata, etc. −
Examples include phenolic couplers having an acylamino group in the position; and nine-naphthol couplers described in Japanese Patent Application No. 2360 and the like.

In order to correct unnecessary sub-absorption existing on the shorter wavelength side of the main absorption of the coloring dye, Yellow 19 may be used in combination with a magenta-colored colored coupler. These couplers are usually prepared using a high boiling point organic solvent such as a 7-talic acid ester or a phosphoric acid ester having carbon number/is~3.2, and if necessary, an organic solvent such as ethyl acetate. It is used by dispersing the emulsion in a medium. Typical amounts of color couplers used are 1 mole of photosensitive silver halide, preferably 0.0 to 0.005 moles for yellow couplers and Fio2 to 0.3 moles for cyan couplers.

(Effects of the Invention) According to the method of the present invention, even if a color developing solution is recycled for a long period of time using an anion exchanger, the photographic properties of the color photosensitive material are extremely stable, and the next image retention is excellent. It is possible to ensure sex.

Therefore, there is no need to discard part of the used color developing solution or replace it with a fresh solution during the process, and it is possible to significantly reduce the waste solution load and the burden of management work.

Example The present invention will be explained in detail below with reference to Examples.

Example 1 A multilayer photographic paper/0/f having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

(Layer coating liquid preparation S) Yellow coupler (ExY-/) and (ExY-2)
10.2p, ip and color image stabilizer (Cpd-
/)≠, 27.2 cc of ethyl acetate and 7.7 cc of high boiling point solvent (8o1v-t) were added to IAp and dissolved, and this solution was mixed with 10% gelatin containing 10% sodium dodecylbenzenesulfonate rcck. Aqueous solution/IJ-c
Emulsify and disperse in c.

This emulsified dispersion and emulsions EM/and EM, 2 were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution. The coating liquid from the second layer to the seventh layer is also
'fA was prepared in the same manner as the layer coating solution. The gelatin hardening agent for each layer is /-oxy-3,! -Diclo o -8-
) using riazine sodium salt.

As the primary thickener, (Cpd-2)'jr: ratio used.

(Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (CP/R). Silver halide emulsions represent coatings t' in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO□) and a bluish dye. ] th layer (evening sensitive layer) Monodisperse silver chlorobromide emulsion (EM/ ) spectrally sensitized with a sensitizing dye (ExS-/) ・ ・ ・ 0.73 With a sensitizing dye (-Exa-/) Spectrally sensitized monodispersed silver chlorobromide emulsion (EMco) 0. /3 Gelatin.../, rYellow coupler (ExY-/) ・O≠≠ Yellow coupler (ExY-2)...0.32 Color image stabilizer (Cpd-//)...0. /lisolvent (8o
1v-/) ・---0,36 Second layer (color mixing prevention layer) Gelatin ・・・O, Tata color mixing prevention agent (cpa-j) ---0, Or Third layer (green sensitive layer) Sensitizing dye Gravity-dispersed silver chlorobromide emulsion spectrally sensitized with (ExS-2, 3) (EM3) ・ ・ ・ O, θj Monodisperse chlorobromide emulsion spectrally sensitized with sensitizing dye (ExS-2, 3) Silver emulsion (EM≠) ・ ・ ・ 0. // Gelatin ・・・1.10 Magenta coupler (ExM-/) ・0.32 Color image stabilizer (cpa-≠) ・・・O6-0 color image stabilizer (Cpd-6) ・・・(7, 77, two-color image stabilizer (
Cpd-1,)...0.03 solvent (8o1v-,
2) -...0. /2 solvent (Solv-j)
・--0,2! No. West m<ultraviolet absorbing layer) Gelatin...7.60 ultraviolet absorber (Cpd-7/Cpd-♂/Cpd-ta=3/co/l
: weighted ratio) ・0.70 Color mixture prevention agent (cpct-10)...0.0! Solvent (S
0.07 Monodisperse silver chlorobromide emulsion (EMj) spectrally sensitized with a sensitive dye (ExS-≠, J') Gelatin 0.1 inch...O, Tercian coupler (ExC-/)...0.32 Color image stabilizer (cpa-♂/Cpd-ta, 'cpa-/,
2=3/41/2: weight ratio) ・0. /7 Polymer for dispersion (cpct-//)...0.21 Solvent (Solv-2) -0,20 No. 61-
(Ultraviolet absorption layer) Gelatin...O1! ≠Ultraviolet absorber (Cpd-7/Cpd-ta/Cpd-/2=//!/
3: Weight ratio) ・O, Col Solvent (So 1v-2) -・-0, Or 7th r
a (WI retaining layer) Gelatin.../233 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 77%) Fluid Nomura Fine 0. /7 ・ ・ ・ 0.03 EX, -/ 5O3HN(C2H5)3 ExS-koExS-7 ExS-j 5U3NH<C2H3)3 ExS-≠ 8(J3) to 1(C2H5)3 At this time, As an anti-irradiation dye,
(Cpd-/3 cpa-/≠) was used.

Further, each layer contains, as an emulsifying dispersant and a coating aid, alkanol B (CDupont), sodium alkylbenzenesulfonate, succinate ester, and Magef.
acx-F −/20 (manufactured by Inu Nippon Ink Co., Ltd.) was used. As a stabilizer for silver halide, (cpa-/!,
/A).

Details of the emulsion used are as follows.

EM/ EM co 8M3 EM≠ Mj ll cube cube cube cube cube cube /, O O,7I O9! 0,≠ Q,! 0,≠ t.

r3 o, or 0.07 0, Ori o,i.

Q,Ori o,i.

The structural formula of the compound used is as follows.

ExY-/ A Diptyl phthalate olv-2 Tricresyl phosphate olv-j Trioctyl phosphate 301v-≠ Trinonyl phosphate Cpd-1 C4) 19(t) Cpd-ta Cpd-10 H cpa-// ShikuJ IN Pi Shi4 M g l I JCpd
-/μ Next, sample 102-10t was prepared by replacing the magenta coupler EXM-/ of sample 10/ with the coupler below.

Sample 102 Cpd-/j cpct-lA Sample 103 α H Sample 70 Hiroshi Specific example M-37 Sample 10! pM-412 Sample 101=#M-AI Sample 10/-10tflr prepared as above,!
After cutting it into strips, it was exposed to light using a printer. Next, using a small automatic developing machine for each sample and regenerating the color developer, the amount of replenishment of the color developer will be three times the capacity of the color development processing tank using the method detailed below. Treatment continued until.

From the start of the above process, each time the color developing tank capacity is replenished (that is, at the time when 0./, λ, 3 times the capacity is replenished), the color temperature 2tj≠ is changed to the exposure t2! OCM
8 wedge exposure samples were processed, magenta sensitivity,
Examination of change sound of minimum concentration, temperature 60℃, relative humidity 70
Next, we investigated the change in the minimum density of yellow after storage for 2 weeks under conditions of %. The results were published in the first volume.

Color development 37℃ 3 minutes 30 seconds 200d bleach fixing 33℃ 7 minutes 30 seconds Yo! -L lA water wash■ 2≠～3℃ 1 minute Column water wash■2μ
～3≠℃ 7 minutes 2L water washing ■2μ～3μ℃ 1
Minutes 10X 2I.

Drying 7 ONfO 0 C for 7 minutes *Photosensitive material/- (3 tank cascade from water washing to ■) The composition of each processing solution is as follows.

water diethylenetriamine pentaacetic acid nitrilo-to, N,N-trimethylenephosphonic acid l-hydroxyethylidene-/,/-diphosphonic acid benzyl alcohol diethylene glycol sodium sulfite 00xl ♂00d /, Of i, op co, Oy co, Oy /, Od /, Od /ld 0IL1 0d co, oy3, op N-ethylhe-(β-methanesulfonamidoethyl)-3-methyl-guaminoaniline sulfate hydroxylamine sulfate fluorescent i brightener (WHITBX<z, /, (manufactured by Sumitomo Chemical) pH (2! ℃) ioottt! ,Ori3,Of/O,CoO Ammonyl thiosulfate (70%) Sodium sulfite 1ILooytz 160w1 13 Tata, Oli≠, jy i, op 000wJ 10, ro μ00m1 00sd 26 Taethylenediamine 139 /10f Iron tetraacetate ( 1000d 1000dp1-
1c2jc) 1. ,． 70 6.30 Recycling method of color developer The color developer 62 was replenished and the recovered overflow liquid ≠, rttt, anion exchange resin (Amberlite IRA- manufactured by Rohm and Haas Co., Ltd.) which had been previously treated as follows. ≠oo) The liquid was passed through a plastic expanded cylindrical column (inner diameter: 2.6, resin layer height: approximately ≠0) filled with rfbk at 20 to 1,000 times per minute, and collected.

This liquid contains benzyl alcohol, diethylene glycol,
When sodium sulfite, heetherhe-(β-methanesulfonamidoethyl)-3-methyl-μm aminoaniline sulfate, hydroxylamine sulfate, optical brightener, and potassium carbonate are concentrated and water is added to create a panoramic zX , was added so as to have the above-mentioned replenisher composition. In addition, diethylenetriaminepentaacetic acid, nitrilo-N,N,N-trimethylenephosphonic acid, the former 2°, 2
The latter was added for ≠, 3y, and the pH was 5 with potassium hydroxide! Adjusted to the same value as the replenisher using c acid.

The psychic solution prepared in this way is used as a replenisher from now on,
Each time z2 replenishment was completed, it was regenerated and used in the same manner as above.

Treatment method for O anion exchange resin Part 1: 0. jM/It sodium hydrogen carbonate solution Otsu 2
was passed through the column at ♂Otg per minute, followed by distilled water tX.
The solution was passed through itog every minute, washed, and used to regenerate the developer.

After the λth time: After using the developer μ and r2 for regeneration, distilled water t
Wash the
1. The liquid was passed through the column at a total rate of 10 d/min, and distilled water 6β was added again.
The solution was passed through the solution at a rate of 1 aOtd per minute, and then treated in the same manner as the first step, and used for regenerating the developer.

As mentioned above, using a coupler other than the present invention, the following sample 10/
~ Regarding 103VC, the variation in magenta sensitivity during playback running is the lowest! The 1 degree fluctuation (minimum density gradually increases from the start, confirmed to increase fog), and
As regeneration continues, house a under high temperature and high humidity storage
- sensitivity according to the invention, whereas an increase in stain occurs;
Fluctuations in minimum density (fog) are extremely small, and at high temperatures,
There is no increase in IA stain under high humidity.

Example 2 A color eater for printing having the layer structure shown below was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows. This is the sample, 2
It was set to 01.

(Preparation of coating solution for the first layer) Yellow coupler (ExY-/)/ri, /ri and color image stabilizer (Cpd-/) Hiroshi, ≠1 ethyl acetate core, 2C
C and high boiling point solvent (8o1v-/)7.7CC(Ir
, 0F) t-add and dissolve this solution, IO% aqueous gelatin solution containing IO% sodium dodecylbenzenesulfonate tccf/r! It was then emulsified and dispersed. This emulsified dispersion and emulsions EM7 and EMt were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. l-oxy-3,j-dichloro-8-triazine sodium triwam salt was used as the gelatin hardening agent for each layer.

Moreover, (cpct-, 2) was used as a thickener.

(Layer structure) The composition of each layer is shown below. Is the number the coating amount C1/rr? )
T-fi. For silver halide emulsions, apply the silver equivalent coating amount.

Support polyethylene laminate paper [The polyethylene on the first layer side contains white pigment (Tie) and Yoi-mi dye. ] th layer (blue-sensitive layer) Monodispersed silver chlorobromide emulsion (EM7) spectrally sensitized with a sensitizing dye (Ext-/) ... o, iz sensitizing dye (Ext-/) Monodisperse silver chlorobromide emulsion (EMf) spectrally sensitized with o, is Gelatin ・・・・・・ /, ♂ Otsuye ○- coupler (ExY-/) 0.12 Color image stabilizer (cpci-, 2) ・・・・・・ 0.
Solvent (Solv-/) = -0,36 second r
fji (color mixing prevention layer) Gelatin ・・・・・・ O, Tata color mixing prevention agent (cpa-g ・・・・・・ OoOza third layer (green sensitive layer) Sensitizing dye (ExS-2, 3) Spectrally sensitized monodisperse silver chlorobromide emulsion (EM) ...0,/- Spectrally sensitized monodisperse silver chlorobromide emulsion (EM) with sensitizing dyes (ExS-2,3) EMlo) Gelatin O, -≠ Ha, 21A Magenta coupler (ExM-/)...0.3 Color image stabilizer (cpct-≠)...Q, 2!
Color image stabilizer (cpa-j) 0.12
Solvent (S-olv-2)...”・0.2!
Fourth layer (ultraviolet absorbing layer) Gelatin ... /, 60 ultraviolet absorber (Cpd-+/cpcl-7/Cpd-r=
3/2/A: heavy illumination ratio)...0.70 Color mixture prevention agent (cpct-ta)...0.02
Solvent (Solv-j) ・・・・・・ O1≠2
Fifth layer (red-sensitive layer) Monodispersed silver chlorobromide emulsion (EM//) spectrally sensitized with a sensitizing dye (ExS-Hiroshi, J'') ...... 0.07 Sensitizing dye ( Monodisperse silver chlorobromide emulsion (EM/j) spectrally sensitized with ExS-Hiro, it Gelatin ・・・・・・ Oo 2 cyan coupler (ExC-/) ・・・・・・ 1 .Hiroshi6 Color image stabilizer (cpa-7/Cpd-77Cpd-10=
3/4t/2 : weight ratio)...O,/7 Polymer for dispersion (Cpd-//) o, i4 as solvent (Solv-/) ・==-0,,20 6th layer ( Ultraviolet absorbing layer) Gelatin, mountain... o, jμ ultraviolet absorber (cpa-g/cpct-r/cpa-10=/
/j/3: Weight ratio)...0. ．． 2/ Solvent (Solv-μ) 0.0? 7th layer (maintaining layer) Gelatin/Mountain... 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 77%) Liquid paraffin 0,/7 0.03 Also, at this time, an anti-irradiation dye and Well, (
cpd-/2, Cpd-/J).

Further, in each layer, as an emulsifying dispersant and a coating aid, Alkanol
xF-/, 20 (manufactured by Inu Nippon Ink Co., Ltd.) was used. As a stabilizer for silver halide, (cpa-/≠, /
I used ri.

Details of the emulsion used are as follows.

EM7 Cube EltdJ’ Cube EM cube EMlo cube EM//　cube EM/2 cube 8/1 0.1 1 0,≠!　　　　1 0.34t 1 0,≠evening l O, 3! /L / , o o, i.

, o o, i.

, j　　　　　　o, ori , 2 0.0ri , j o, ori , t o, i.

−? FJ+r1su The structural formula of the compound used is as follows.

ExY-/ ／’／ ExM-/ ExS-j ExS-j ExC-/ ExS-/ ExS-2 Cpd-/ Cpd-2 Cpd-J To SO3M (02)15)3 ! to 5(73)4(C2H5)3 H Cpd-Hiroshi Cpd-j cpct-+ C4) 1゜ (tl Cpd-// C0III)iC4H9(I) cpd-7,2 cpd-i3 cpd-7 C4M.

(tJ Cpd -7f cpd-2 cpd-10 CI-J 2CH2C(, T(JC8)1,.

Cpd-i≠H Cpd-/! H o1 V-/ dibutyl phthalate Soo V- cotrioctyl phosphate o1v-J trinonyl phosphate So breath V-≠ tricresyl phosphate Next sample 07 magenta coupler EXM-i 7 Directly replace the sample below with the coupler - Oko λOr was produced.

Sample Ko O2 α Sample 20! Sample size Oμ Specific example M-37 Sample, 20! Specific example M-4t sample 20t Specific example M-A! r Sample iθ7 Specific example M-30 Sample 2 or Specific example M-67 Tabulated as above and processed in the same manner as Example -/ except for the following in the next sample, 20/-206, and the result was Kinshi λ Shown in the table below.

'lJ image 3j℃ 4tj seconds /it/d
/71 bleach xa 3o ~ 3t"c 4tr seconds
1ittt /712 stable■30~37℃ 2o seconds
□ / Q1 stable ■ 30-37℃, 2 (7 seconds □ 10
7! Stable ■ 30-37℃ 20 seconds □ 1012 Stable ■
3.0~37℃ 30$) 24#wt 10IL dry
Drying 7Q-♂z℃ to seconds * Sensing material irr? The composition of each treatment liquid is as follows.

Color developer water tank liquid 00d Ethylenediaminetetraacetic acid! , 6-dihydro-a-xybenzene-l, co-protected trisulfonic acid triethanolamine co-protected, OF 0.3 nor, oy N-ethyl-(β-methanesulfonamidoethyl)-3-methyl-couaminoaniline Sulfur salt diethylhydroxylamine s, oy hiro, 2F replenisher 00d, QF 0.37? , Oy 7, Of optical brightener (CIBA, 2. OF) Add water to 10004 1000ydpH (
jj'c) 10. Oj 10.4t! Bleach-fix f (tank solution and refill solution are the same) water
≠00td Ammonium thiosulfate 100yd (70%) Sodium sulfite /7y Iron ethylenediaminetetraacetate! ! 1 (l [l) ammonium ethylenediaminetetraacetic acid dijy sodium t,oy Add water to pH (2j℃) Stabilizing solution (tank solution and replenishment solution are the same) Formalin (J7%) Formalin-sulfite adduct - black mouth -Komechi-≠- ooow! ,≠0 o,ip O,7riO,Oλy isothiazoline-3-oncomethyl-≠-isothiazo o,oiy phosphorus-3
- Add water to iooowpH (j
j°C) 4L, 0 Furthermore, in the processing of this example, the amount of t carried into the safety process of the bleach-fixing solution was ≠Od per 1 trt of the light-sensitive material.

Method for regenerating color developer The method was carried out in the same manner as in Example 7, but the component analysis of the color developer after anion exchange treatment was conducted using diethylhydroxylamine, heether-N-(β-methanesulfonamidoethyl)-3-methyl- ≠ - Performed for aminoaniline sulfate, potassium carbonate, optical brightener, triethanolamine, and for others, for prepared replenisher 62, ethylenediaminetetraacetic acid ≠, 31! ,j,ip-dihydroxybenzene-/,2. ≠-Trisulfonic acid o, tp was added.

Further, pn was made the same value as the replenisher using potassium hydroxide and sulfuric acid.

Anion exchange resin treatment method 1st session: Same as Example-/ 3rd session and thereafter: The treatment with sodium chloride solution and the subsequent washing steps in Example-7 are deleted, and the rest are the same as Example-1. I went to

Example 3 In Example 2, the following example was carried out using the same amount of the following compound instead of diethylhydroxylamine in the color developing solution.
As a result of performing the same operation as in Table λ, substantially the same results as shown in Table λ were obtained.

As a result, the same results as in Table 2 were obtained.

In addition, the stabilizing solution of Example 2 was washed with water at a temperature of 30° C. and a water amount of 317 minutes, and the results were the same as in Table 2, with 6 results.

Patent applicant: Fuji Photo Film Co., Ltd. Example-≠ In Example-2, the stabilizing solution was treated to have both calcium and magnesium below J"l/It, and deionized water (conductivity λ
μS/am) Written amendment to the procedure related to the case by a person who amends the name of the claimed invention in a similar case by changing K (spontaneous) 1938 Patent Application No. -t≠try Silver halide color photographic light-sensitive material How to process

Claims (1)

[Scope of Claims] A color developer used in processing a silver halide color photographic material containing at least one type of pyrazoloazole magenta coupler represented by the following general formula (I) is brought into contact with an anion exchanger. 1. A method for processing a silver halide color photographic light-sensitive material, which method is then reused for processing the silver halide color photographic light-sensitive material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a coupling reaction with an oxidized aromatic primary amine developer. Represents a group that can leave.Za, Zb
and Zc is methine, substituted methine, =N- or -NH
-, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where Zb-Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Furthermore, 2 with R_1 or X
It also includes the case where a multimer of more than one mer is formed. Also, Za,
When Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer. )