JPS63170643A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the stability of the developer, and to reduce remarkably the increasement of the fog at the time of continuously processing, by processing the exposed titled material with a developer contg. at least one kind of a specific hydrazine. CONSTITUTION:The exposed silver halide photographic sensitive material is processed with the developer contg. at least one kind of the hydrazine shown by formula I wherein X is a divalent group selected from -CO- and -SO2- groups, etc., R<1> is hydroxyl, hydroxyamino, carbamoyl, hydradinocarbonyl, amino, or hydrazino group, R<2> is hydrogen atom, alkyl or aryl group, R<1> and R<2> together with each other may form the dimer or the polymer more than the dimer, by the group R<1> and R<2>, but, when X is -CO- group, R<1> is not hydrazino group. Thus, the increasement of the fog and the change of the gradient are remarkably reduced, and the image having excellent photographic characteristics is obtd., even in case of processing the exposed silver halide photographic sensitive material with the developer after secular preservation.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for processing silver halide photographic materials, and in particular improves the stability of the developer and reduces fog during continuous processing. The present invention relates to a processing method that significantly reduces

(Prior Art) Color developers using aromatic primary amine color developing agents have long been used in color image forming methods, and currently play a central role in color photographic image forming methods. .

However, the color developer mentioned above is very easily oxidized by air and metals, and when a color image is formed using an oxidized developer, fog increases, sensitivity and gradation change, and desirable photographic characteristics cannot be obtained. This is well known.

Therefore, various means for improving the retention properties of developing solutions have been studied, and among them, the most common method is to use hydroxylamine and sulfite ions in combination. However, when hydroxylamine is decomposed, ammonia is generated.
Sulfite ions cause fogging, and sulfite ions act as competing compounds for developing agents, inhibiting color development, and are therefore not suitable preservatives.

In addition, various preservatives and chelating agents have been studied in order to improve the stability of color developers. For example, as a preservative, JP-A-52-49828,
Aromatic polyhydroxy compounds described in US Pat. No. 9-160142, US Pat. No. 56-47038, and US Pat. No. 3,746.544, US Pat. No. 3.615,503 and British Patent No. 1.306.176. Hydroxycarbonyl compounds described in JP-A-52-143020 and JP-A-53-8
Examples thereof include α-aminocarbonyl compounds described in JP-A-54-3532, metal salts described in JP-A-57-44148 and JP-A-57-53749, and the like. In addition, as a chelating agent, Japanese Patent Publication No. 4B-30496 and No. 44-30232
Aminopolycarboxylic acids described in JP-A-56-973
No. 47, Special Publication No. 56-39359 and West German Patent No. 2,
Organic phosphonic acids described in No. 227.639, JP-A-52
-102726, 53-42730, 54-1
No. 21127, No. 55-126241 and No. 55-6
Examples include phosphonocarboxylic acids described in JP-A-58-195845, JP-A-5B-203440, and JP-B-Sho 53-40900.

However, even if these techniques are used, the preservation performance may be insufficient or the photographic properties may be adversely affected.
No satisfactory results have been obtained.

In particular, in color developers from which benzyl alcohol, which is harmful due to pollution and liquid preparation, has been removed, the coloring performance inevitably deteriorates, but in such systems, the preservatives that act as competing compounds are In order to significantly inhibit color development,
Many of the techniques considered in the past are unsatisfactory.

Furthermore, color photographic materials containing silver chlorobromide emulsions with a high chlorine content tend to cause fogging during color development, as disclosed in JP-A-58-95345 and JP-A-59-232342.
listed in the number. When using such emulsions, a preservative that is less soluble in the emulsion and has better preservative performance is essential, but no preservative that is satisfactory in this sense has yet been found. .

(Objective of the Invention) Therefore, an object of the present invention is to provide a method for processing a photosensitive material in which the stability of the developer is excellent. Another object of the present invention is to provide a processing method in which an increase in fog during continuous processing is significantly reduced. Still another object of the present invention is to provide a processing method with excellent color development.

(Structure of the Invention) The above object was achieved by the method described below.

After exposure, a silver halide photographic light-sensitive material is prepared using the following general formula (1).
1. A method for processing a silver halide photographic light-sensitive material, which comprises processing with a developer containing at least one hydrazide represented by the following.

General formula (I) represents a divalent group selected from R1-X-NHNH-R2. The total represents a hydroxyl group, a hydroxyamino group, a carbamoyl group, a hydrazinocarbonyl group, an amino group, or a hydrazino group, and R2 represents a hydrogen atom, an alkyl group, or an aryl group. A dimer or more multimer may be formed by the substituents R' and R''.However, when X is 100-, R'
does not become a hydrazino group. ) -a The hydrazides represented by formula CI) will be explained in detail below.

Represents a divalent group selected from, R■ is a hydroxyl group,
hydroxyamino group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted hydrazinocarbonyl group,
Substituted or unsubstituted amino group (preferably 0 to 0 carbon atoms)
10, for example, amino group, diethylamino group, dipropylamino group, hexylamino group, anilino group, naphthylamino group, etc.), or substituted or unsubstituted hydrazino group (preferably 0 to 10 carbon atoms, for example, N', N'
-dimethylhydrazino group, N'-phenylhydrazino group, etc.) R2 represents a hydrogen atom, a substituted or unsubstituted alkyl group (preferably 1 to 10 carbon atoms, such as methyl group, ethyl group, cyclohexyl group, methoxy ethyl group, etc.), or a substituted or unsubstituted aryl group (preferably having 6 to 10 carbon atoms, for example, phenyl group, 3-hydroxyphenyl group, etc.).

Groups to be further substituted with substituent R1 include alkyl groups, aryl groups, halogen atoms (chlorine, bromine, etc.), hydroxyl groups, carboxyl groups, sulfo groups, amino groups, alkoxy groups, amide groups, sulfonamide groups, and carbamoyl groups. , sulfamoyl group, aryloxy group, alkylthio group, arylthio group, acyl group, nitro group, cyano group,
Preferred are a ureido group, a sulfonyl group, a sulfinyl group, a hydrazinocarbonylamino group, a hydrazinocarbonyloxy group, and when there are two or more substituents, they may be the same or different, and these substituents may be further substituted. It's okay.

Examples of groups to be further substituted with substituent R2 include halogen atoms (chlorine, bromine, etc.), hydroxyl groups, carboxyl groups, sulfo groups, amino groups, alkoxy groups, amide groups, sulfonamide groups, carbamoyl groups, sulfamoyl groups, alkyl groups, Aryl groups are preferred, and they may be further substituted.

In general formula (I), -CO- is preferable as X.

-a Formula CI), preferred as R1 is an amino group, particularly an arylamino group, an alkylamino group, an alkenylamino group, and especially an arylamino group (preferably a carbon number of 10 or less, such as a phenylamino group) , naphthylamino group, etc.), and these may be substituted. Examples of the substituent include the same substituents as those for R1. When there are two or more substituents, they may be the same or different, and these substituents may be further substituted. Preferred substituents include a carboxy group, a sulfo group, a hydroxy group, an alkoxy group, a sulfonamido group, a sulfamoyl group, a hydrazinocarbonylamino group, and a carboxy group, a sulfo group, and a hydrazinocarbonylamino group are particularly preferred.

In general formula (1), R2 is preferably a hydrogen atom or an alkyl group, and most preferably a hydrogen atom.

When the compound represented by general formula (1) is a monomer, the total number of carbon atoms is preferably 15 or less, and 10
It is more preferably 7 or less, most preferably 7 or less.

The compound of general formula (I) may form a bis body, a tris body, or a polymer linked by R1 or Rt.

Specific examples of the compound represented by general formula (1) are listed below, but the present invention is not limited thereto.

(I 1 ) N Ht N HCON HzH (I-2,) NHt NHCNH! (I 3
) N Ht N HCON HN Hz (I-4
) NH,NH30,H (1-5) N)IzNH3OzNHNHz(1-
6) NHtN)(CONHOHH (I 8) CHsNHNHCNHz(1-9)
CH3NHN)130□N)IN)ICH.

NHzNHCONH(C)lzh NICONI(N
) 1g (I-12) NH1NHCONHCH2 (
I-13) (I-14) NHzNH3OxNHOH(I-1
5) (1-16) NH! N) ICONI(CON)IN
)1! (I-19) (121) N1(tcOcONHNHz(1-22
) NHtNHCOCONHNHz (I-24) (I-31) Nti (JNtlNtit (I-38) (I-44) (, I-50) (1-53).

NaOxSCH*CHtNHCNHNHt(1-54)
.

H00CCHt CHz N HCN HN H! CH
s N HN HCN HN HCHsHOOCCHz
CHJHNHCNHN)lcTocHzcOOHNaO
sSCHzCHzCHJ)INHCNHNHCHHzC)
IzCHzSOzNa Many of the compounds represented by the general formula (1) are available as commercial products, and are also available in "Organic Synthesis J"
ntheses), Co11°Vol, 2. p228
, “New Experimental Chemistry Course”, Volume 14, ■.

p 1621-162B (Maruzen) s Be11. +
2+ 559, Be11. .

It can be synthesized according to general synthesis methods such as No. 3 and 117.

These compounds represented by the general formula (1) may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, Scheller's acid, and acetic acid.

The amount of the compound represented by the general formula (1) to be added to the developer is 1.5 x 10" mol to 3.5" mol per 11 of the developer.
Ox 10-' mol, preferably 5.0 x 10-'
1 to 3 moles. Ox is 10-' mol.

As the developer used in the present invention (for example, a color developer, a black and white developer), any known developer can be used. The black and white developer contains dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. l-phenyl-
3-pyrazolidone), aminophenols (e.g. N-
Known developing agents such as (methyl-p-aminophenol) can be used alone or in combination.

The following description will focus on color developing solutions.

The color developer used in the present invention contains a commonly used aromatic primary amine developing agent. In particular, the following aromatic primary amine developing agents are preferred.

(A-1) 2-methyl-4-[N-ethyl-N-(
β-hydroxyethyl)aminocoaniline (A-2) N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline In addition, these aromatic primary amine developing agents are sulfate salts. , hydrochloride, sulfite, p-toluenesulfonate, and other salts.

Furthermore, the compounds (A-1) and (A-2) above may be used in combination of two types, or may be used in combination with other aromatic primary amine color developing agents as necessary. good.

The amount of aromatic-grade amine developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.1 g to about 20 g per 1 liter of developer solution.
Concentrations range from 5g to about log.

Examples of using hydrazides in color developers include U.S. Pat. Nos. 3,141,771 and 2,772.
．． Although it is described in No. 973, sufficient preservability cannot be obtained, and by using the hydrazide represented by the general formula (1) of the present invention instead, the preservability is significantly improved and the occurrence of fog is suppressed. This is noteworthy.

The color developer used in the present invention is shown below.

The color developer used in the present invention preferably does not contain hydroxylamine. Even when it is contained, it is preferable that the amount added is as small as possible.

Further, from the viewpoint of preventing fogging, it is preferable that benzyl alcohol is substantially not contained. "Substantially no benzyl alcohol is contained" means that the amount of benzyl alcohol is 2 ml or less per liter of color developer. Preferably, it does not contain any benzyl alcohol.

In addition, as other preservatives, 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 amount added to these color developers is 1.0
g/j! It is preferably 0.5 g/l or less. When the preservative of the present invention is used in a color developer that does not contain benzyl alcohol, it is preferable that the amount of sulfite ion added be small in terms of preservability and/or photographic properties.

Other preservatives include U.S. Patent No. 3. 615. 503
Hydroxyacetones described in British Patent No. 1.306,176, JP-A-52-143020 and JP-A-53
-89425, various metals described in JP-A-57-44148 and JP-A-57-53749, various I! described in JP-A-52-102727, etc. hydroxamic acids described in No. 52-27638, α,α'-dicarbonyl compounds described in No. 59-160.141, salicylic acids described in No. 59-180588, alkanolamines described in No. 54-3532, Poly(alkylene imine)s described in No. 56-94349, gluconic acid derivatives described in No. 56-75647,
Examples include tertiary cyclic amines described in Japanese Patent Application No. 62-265149. Two or more of these preservatives may be used in combination, if necessary.

Particularly preferred is the addition of alkanolamines (triethanolamine, jetanolamine, triethylenediamine (1,4-diazabicyclo[2,2,2]octane), etc.) and/or aromatic polyhydroxy compounds.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, 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 hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/2
It is preferable that it is more than 0. 1 mol/l~0
．． Particularly preferred is 4 mol/l.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer.

The chelating agent is preferably an organic acid compound, such as the aminopolycarboxylic acids described in Japanese Patent Publication No. 4B-30496 and Japanese Patent Publication No. 44-30232, Japanese Patent Publication No. 56-97347, Japanese Patent Publication No. 56-39359, and West German Patent No. 2. 227
．． Organic phosphonic acids described in No. 639, JP-A-52-10
No. 2726, No. 53-42730, No. 54-1211
No. 27, No. 55-126241 and No. 55-6595
Phosphonocarboxylic acids described in No. 6, etc., and other JP-A No. 1973
Examples thereof include compounds described in Japanese Patent Publication No. 8-195845, No. 58-203440, and Japanese Patent Publication No. 53-40900. 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, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid , l-hydroxyethylidene-1゜l-diphosphonic acid, N, N'-bis(2-hydroxybenzyl)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 0.1 g to Log per liter.

Any development accelerator can be added to the color developer if necessary. As a development accelerator,
No. 16088, No. 37-5987, No. 38-7826
No. 44-12380, No. 45-9019, and U.S. Patent No. 3,813,247, etc.;
p-phenylenediamine compounds shown in No. 15554, JP-A-50-137726, JP-B No. 44-30
No. 074, JP-A-56-156826 and JP-A No. 52-4
3429, etc., U.S. Patent Nos. 2,610,122 and 4,119.46
p-aminophenols described in No. 2, U.S. Patent Nos. 2 and 4
No. 94.903, No. 3゜128.182, No. 4,23
No. 0,796, No. 3.253,919, Special Publication No. 1977-
No. 11431, U.S. Patent No. 2,482,546, No. 2
, 596.926 and 3,582,346, etc., Japanese Patent Publication No. 37-16088, 4
No. 2-25201, U.S. Patent No. 3,128.183,
Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3. 532. Polyalkylene oxide represented by No. 501, other 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

The color developer used in the present invention may include, if necessary,
Any antifoggant can be added. 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-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2
Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, hydroxyazaindolizine, 5-nitroindazole, and mercaptotriazoles.

The color developer used in the present invention preferably contains a fluorescent brightener. As a fluorescent whitening agent, 4.4'-
Diamino-2,2'-disulfostilbene compounds are preferred, the amount added is 0 to 5 g/2, preferably 0.1 g to 4
g/l.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40'C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. It is preferable that the amount of replenishment is small, but 20 to 600 mj per 1M of photosensitive material! Preferably 50-300mj! It is. More preferably 100
rrl~200mj! It is.

Next, the bleaching solution, bleach-fixing solution, and fixing solution used in the present invention will be explained.

As the bleaching agent used in the bleaching solution or bleach-fixing solution used in the present invention, any bleaching agent can be used, but in particular organic complex salts of iron (III) (e.g., aminopolymers such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) can be used. Preferred are carboxylic acids, complex salts of aminopolyphosphonic acids, phosphonocarboxylic acids, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide, and the like.

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids useful for forming organic complex salts of iron (I[[),
Aminopolyphosphonic acids, organic phosphonic acids, or salts thereof include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid,
Cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Examples include iminodiacetic acid, 1-hydroxyethylidene-1°1-diphosphonic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron(III) ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodiacetic acid
Complex salts are preferred because they have a high bleaching edge.

These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. It may be used in excess. Among iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/l, preferably 0.05
~0.50 mol/2.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, U.S. Patent No. 3,893,858, West German Patent No. 1,
Compounds having a mercapto group or disulfide bond described in No. 290.812, JP-A-53-95630, Research Disclosure Na17129 (July 1978), JP-A No. 45-8506, JP-A-52
-20832, No. 53-32735, U.S. Patent No. 3
．． Thiourea compounds described in No. 706,561, or halides such as iodine and bromide ions are preferable because they have excellent bleaching properties.

In addition, the bleach or bleach-fix solution used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides. (
For example, a rehalogenating agent such as ammonium iodide) may be included. If necessary, it has a pH buffering capacity of boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. 1
More than one type of inorganic acid, organic acid, alkali metal or ammonium salt thereof, or a corrosion inhibitor such as ammonium nitrate or guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; a thiocyanate such as sodium thiocyanate or ammonium thiocyanate; or ethylene. Bisthioglycolic acid, 3,6-cythia 1
．． These are water-soluble silver halide dissolving agents such as thioether compounds such as 8-octanediol and thioureas, and these can be used alone or in combination of two or more. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of fixing agent per 11 is preferably 0.3 to 2 moles, more preferably 0.3 to 2 moles. It is in the range of 5 to 1.0 mol.

The pH range of the bleach-fix solution or fix solution in the present invention is 3 to 3.
10 is preferable, and 5 to 9 are particularly preferable.

Further, the bleach-fix solution may contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fixing solution and fixing solution in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, bisulfite, etc.) as preservatives. potassium, etc.), metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.).

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

Next, the water washing step in the present invention will be explained.

In the present invention, it is also possible to use a simple treatment method such as performing only a so-called "stabilization treatment" without providing a substantial water washing step instead of the usual "water washing treatment". "Water washing treatment" is used in the broad sense described above. In addition, the "washing process" here includes water washing alternative processes such as rinsing process.

The amount of washing water in the present invention is difficult to specify because it varies depending on the number of baths in multistage countercurrent washing and the amount of pre-bath components brought into the photosensitive material. It is sufficient if the liquid component is 1×10 −4 mol/2 or less. For example, in the case of 3-tank countercurrent water washing, the photosensitive material 1
It is preferable to use about 1000 ml or more per nl, more preferably 5000 rr1 or more. In addition, in the case of water saving treatment, 100 to 1000 mj per rrl of photosensitive material.
! Good to use.

Washing temperature is 15°C to 45°C, more preferably 20″C
~35°C.

In the washing process, for the purpose of preventing sedimentation and stabilizing the washing water,
Various known compounds may be added. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid; bactericidal agents and anti-piping agents that prevent the growth of various bacteria, algae, and molds. For example, "Journal of Antibacterial and Antifungal Agents"
, Agents), Vol. 11° 5. p2
07-223 (1983) and the compounds described in Hiroshi Horiguchi's "Chemistry of Antibacterial and Antifungal", metal salts such as magnesium salts and aluminum salts, alkali metal and ammonium salts, or dry load and unevenness. A surfactant or the like may be added as necessary to prevent this.

Or West's ``Photographic Science and Engineering Magazine (Photo.

A compound described in Sci.

Furthermore, the method of reducing calcium ions and magnesium ions described in Japanese Patent Application No. 131632/1988 can be effectively used to prevent water from spoiling.

Furthermore, chelating agents, bactericides, and anti-piping agents are added to the washing water.
The present invention is particularly effective when the amount of washing water is significantly reduced by performing two or more types of multi-stage countercurrent washing. It is also particularly effective when carrying out a multi-stage countercurrent stabilization process (so-called stabilization process) as described in JP-A-57-8543 instead of the usual water washing process. In these cases, the bleaching and fixing components in the final bath may be at most 5XIO-'' mol/2, preferably at most 1XIO-'' mol/2.

Various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, adjust the membrane pH (e.g. pH 3~
8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) (used in combination) and aldehydes such as formalin are representative examples. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (thiazole series, isothiazole series, halogenated phenols, sulfanilamide, benzotria, sol) ), surfactants, fluorescent brighteners, hardeners, and other various additives may be used, and two or more compounds for the same or different purposes may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storage stability.

When the amount of washing water is significantly reduced as described above, some or all of the overflow liquid of washing water may be allowed to flow into the bleach-fixing bath or fixing bath, which is a pre-bath, as a drain! Preferable for the purpose of reduction.

In this treatment step, during continuous treatment, a constant finish can be obtained by using a replenisher for each treatment solution to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring, etc., as necessary.

The method of the present invention can be applied to any processing step that uses a developer. For example, it can be applied to the processing of black and white photosensitive materials in addition to color photosensitive materials such as color paper, color reversal paper, color positive film, color negative film, color reversal film, and color direct positive photosensitive materials (eg, paper).

The silver halide emulsion of the light-sensitive material used in the present invention can have any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide, silver chloride, etc., but when performing rapid processing or low replenishment processing For this purpose, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol % or more of silver chloride is preferable, and a silver chloride content of 80 to 100 mol % is particularly preferable. In addition, when high sensitivity is required and capri during production, storage, and/or processing must be kept particularly low, silver chlorobromide emulsions containing 50 mol% or more of silver bromide or Silveride emulsions are preferred, and more preferably 70 mol% or more. If silver bromide exceeds 90 mol %, rapid processing becomes difficult, but there are ways to accelerate development, such as using a development accelerator such as a silver halide solvent, fogging agent, or developer as described below during processing. By using , it is possible to speed up the development to some extent without being limited by the content of silver bromide.
It may be preferable. In either case, it is not preferable to contain a large amount of silver iodide, and it is sufficient if the content is 3 mol % or less. These silver halide emulsions are preferably used mainly for color papers and the like. Color photosensitive materials for photography (negative film, reversal film, etc.) contain silver iodobromide,
Silver chloroiodobromide is preferred, where the silver iodide content is between 3 and 15
Mol% is preferred.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain, or may have different phases. They may be mixed.

The grain size distribution of the silver halide grains used in the present invention may be narrow (or wide), but it is determined by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size (variation rate). ) is within 20%, particularly preferably 15%
So-called monodispersed silver halide emulsions within the following are preferably used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity (monodispersity is defined as the above-mentioned type). (preferably one with a variable rate) can be mixed in the same layer or coated in a separate layer. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, rhombidodecahedral, dodecahedral, etc.).
r) crystals or coexistence of these crystals, or irregular (irregular) crystals such as spherical
It may have a crystalline form (ular), or it may have a composite form of these crystalline forms. Further, tabular grains may be used, and in particular, an emulsion may be used in which tabular grains having a length/thickness ratio of 5 or more, particularly 8 or more occupy 50% or more of the total projected area of the grains. An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is Re5earchDi
sclosure+ vol, 170+ Item N
o, 17643 (1, ■, ■) (December 1978).

In addition, emulsions prepared by the so-called conversion method, which involves a process of converting silver halide already formed before the completion of the silver halide grain formation process to silver halide with a smaller solubility product, and Emulsions which have undergone similar halogen conversion after the completion of the silver grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting and chemical ripening before being used for coating.

Known silver halide solvents (e.g. ammonia, rhodankali or U.S. Pat. No. 3,271,157;
1-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717, JP-A-54-155828, etc.) by precipitation, It can be used for physical ripening and chemical ripening. In order to remove soluble silver salts from the emulsion after physical ripening, washing with water, flocculation sedimentation, ultrafiltration, etc. are used.

The silver halide emulsion used in the present invention contains active gelatin and sulfur-containing compounds that can react with silver (for example, thiosulfate,
Sulfur-enhanced method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); metal compounds ( For example, in addition to total complex salts, a noble metal sensitization method using complex salts of metals in group 1 of the periodic table, such as Pt, Ir, Pd, Rh, and Fe, can be used alone or in combination.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

Additives used in such processes are described in Research Disclosure, Vol. 176, Na17643 (1978).
18716 (December) and volume 187 of the same, Sou 18716 (19
(November 1979), and the relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the above two Research Disclosures, and the locations are shown in the table below.

-Additional friend topic-RD 17643 RD 18716
1 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 4 Brighteners Page 24 5 Antifogging agents Pages 24-25 Page 649 Right column and stabilizers 6 Coupler Page 25 7 Organic solvents Page 25 9 Anti-stinting Agent Page 25, right column Page 650, left to right column 1
0 Dye image stabilizer page 25 11 Hardener page 26 page 651 left column 1
2 Binder Page 26 Same as above 13 Plasticizer, lubricant Page 27 Page 650 Right column 14 Coating aid, pages 26-27 Same as above Surface active agent 15 Static prevention Page 27 Same as above Sensitizing dyes are used to prevent chemical sensitization during particle formation. It may be added before or after, during chemical aggravation, or at any stage during application. Addition during particle formation is effective not only to strengthen adsorption but also to control crystal shape and internal structure of particles. Furthermore, addition during chemical sensitization is effective not only to strengthen adsorption but also to control chemical sensitization sites and prevent crystal deformation. These addition methods are particularly effective in the case of emulsions containing a high content of silver chloride.
Furthermore, it is particularly useful to apply this method to grains with increased silver bromide or silver iodide content on the grain surface.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group can reduce the amount of silver coated than a four-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2.40
No. 7,210, No. 2.875.057 and No. 3
, No. 265.506, etc. The use of two-equivalent yellow couplers is preferred for the present invention; U.S. Pat.
No. 3,933,501 and No. 4. 022゜6
20, etc., or Japanese Patent Publication No. 55-10739, U.S. Patent No. 4
, No. 401,752, No. 4,326.024, RD
18053 (April 1979), British Patent No. 1.42
No. 5,020, West German Application Publication Box No. 2,219,917,
Same 2nd. 261. No. 361, same No. 2.329, 58
Typical examples include the nitrogen atom separation type yellow couplers described in No. 7 and No. 2 433.812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. Same No. 2゜3
No. 43.703, No. 2,600,788, No. 2,
No. 908,573, No. 3,062,653, No. 3
, No. 152,896 and No. 3゜936.015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or U.S. Pat.
, 897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369,879, preferably pyrazolo(5,1-c)(1,2,4) 1-lyazoles as described in U.S. Pat. 24220
(June 1984) and Research Disclosure 24230 (19
In terms of low yellow side absorption and light fastness of color-forming dyes, imidazo (
1,2-b) Pyrazoles are preferred, as described in European Patent No. 11
Pyrazolo (1°5-b) (1,2
, 4)) Riazole are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol couplers and phenolic couplers, preferably the naphthol couplers described in U.S. Pat. No. 2,474°293, and preferably U.S. Pat.
, No. 212, No. 4゜146.396, No. 4,22
Typical examples include the oxygen atom elimination type two-equivalent naphthol couplers described in No. 8.233 and No. 4,296,200. Specific examples of phenolic couplers include U.S. Pat. No. 2,369,929 and U.S. Pat.
No. 01,171, No. 2. 772. No. 162, No. 2,895,826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are typically described in U.S. Pat.
72,002, a phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus, and U.S. Pat. No. 2,772.162;
No. 758.308, No. 4,126,396, No. 4
, No. 334,011, No. 4. No. 327゜173, West German Patent Publication No. 3,329,729 and JP-A-59-
2,5-diacylamino substituted phenolic couplers such as those described in US Pat. No. 166,956 and U.S. Pat.
No. 6,622, No. 4.333.999, No. 4.
451. These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in No. 559 and No. 4,427,767.

In particular, in the treatment method of the present invention, the following general formula (C-1
) By using one type of cyan coupler, it is possible to obtain good photographic properties with less capri. Such an effect is noteworthy.

General formula (C-1) will be explained in detail below.

General formula (C-1) (wherein R11 represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group.

Rlt represents an acylamino group or an alkyl group having 2 or more carbon atoms, and 8 items represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. Further, RI3 may be combined with Rlt to form a ring. Zll represents a hydrogen atom, a halogen atom, or a group capable of leaving in a reaction with an oxidized product of an aromatic primary amine color developing agent.) In general formula (C-1), R11 is an alkyl group having 1 to 32 carbon atoms; Examples include methyl group, butyl group, tridecyl group, cyclohexyl group, allyl group, etc.
Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a 2-pyridyl group and a 2-furyl group.

When R11 is an amino group, W and a phenyl-substituted amino group which may have a substituent are particularly preferred.

R11 further represents an alkyl group, an aryl group, an alkyl or aryloxy group (for example, a methoxy group, a dodecyloxy group, a methoxyethoxy group, a phenyloxy group,
．． 4-tert-amylphenoxy group, 3-tar
t-butyl-4-hydroxyphenyloxy group, naphthyloxy group, etc.), carboxy group, alkyl or arylcarbonyl group (e.g., acetyl group, tetradecanoyl group, benzoyl group, etc.), alkyl or aryloxycarbonyl group (e.g., methoxycarbonyl group,
phenoxycarbonyl group, etc.), acyloxy group (e.g. acetyl group, benzoyloxy group, etc.), sulfamoyl group (e.g. N-ethylsulfamoyl group, N
-octadecylsulfamoyl group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl group, N-methyl-
dodecylcarbamoyl group, etc.), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group, etc.), acylamino group (e.g., acetylamino group, benzamide group, ethoxycarbonylamino group, phenylaminocarbonylamino group, etc.), Imide group (
For example, succinimide group, hydantoinyl group, etc.)
It may be substituted with a substituent selected from a sulfonyl group (eg, methanesulfonyl group), a hydroxy group, a cyano group, a nitro group, and a halogen atom.

In general formula (C-1), Z represents a hydrogen atom or a coupling-off group, examples of which include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.),
Alkoxy groups (e.g., dodecyloxy, methoxycarbamoylmethoxy, carboxypro and ruoxy groups,
methylsulfonylethoxy group, etc.), aryloxy group (e.g., 4-chlorophenoxy group, 4-methoxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetrazocatyloxy group, benzoyloxy group, etc.), sulfonyloxy group groups (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide groups (e.g., dichloroacetylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy groups (e.g., ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy group, etc.), aliphatic or aromatic thio group (e.g., phenylthio group, tetrazolylthio group, etc.), imide group (e.g., succinimide group, hydantoinyl group) These leaving groups are useful for photography. may contain groups.

R11 or R1 of general formula (C-I)! may form a dimer or a multimer.

Specific examples of the cyan coupler represented by the general formula (C-I) are listed below, but the present invention is not limited thereto.

(C-1) ShiL (C-2) Shiki (C-3) (C-4) ShiL (C-5) (C-6) (t) CiH+t (C-7) OH (t) C *H+5 (C-13) ShiL (C-14) ShiL (C-15) (C-16) 0tium Hs (C-17) (C-18) n ShiL (C-19) (C- 20) H (C-21) H (t)Cs)(+1 (C-22) H (t)CsH++ ■ OCR* (C-25) .□ (t)CaH+q (t) CsHl+ These general formulas (C- The coupler represented by 1) is published in Japanese Patent Application Publication No. 5
It can be synthesized based on No. 9-166956 and Japanese Patent Publication No. 49-11572.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive couplers are magenta couplers in U.S. Pat. No. 4,366.237 and British Pat. , 234.533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,82.
No. 0 and No. 4.080°211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4.367.2.
It is described in No. 82.

The various couplers used in the present invention can be used in combination in two or more layers in the same photosensitive layer, or in two or more different layers using the same compound, in order to satisfy the characteristics required for the photosensitive material. It can also be introduced into

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. An example of a high boiling point organic solvent used in the oil-in-water dispersion method is U.S. Pat. No. 2,322,027.
It is written in the number etc.

Further, the process, effects, and specific examples of latex for impregnation of latex dispersion methods are described in U.S. Pat. It is written in the number etc.

Typical usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.1 mole for yellow couplers.
5 moles, 0.003 to 0.00 for magenta couplers.
3 moles, and 0.002 to 0 for cyan couplers.
．． It is 3 moles.

The photosensitive material used in the present invention contains hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenol derivatives, etc. as color antifogging agents or color mixing inhibitors. May contain.

Known anti-fading agents can be used in the photosensitive material used in the present invention. Organic antifading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, and methylenedioxybenzene. Typical examples include aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Also (bissalicylaldoximate)
Metal complexes such as nickel complexes and (bis-N, N-dialkyldithiocarbamate) nickel complexes can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Pat. No. 4,268,593,
Compounds having a hindered amine and a hindered phenol structure in the same molecule give good results. In addition, in order to prevent the deterioration of magenta dye images, especially the deterioration caused by light, the substitution of spiroindanes as described in JP-A-56-159644 and hydroquinone diether or monoether as described in JP-A-55-89835 is recommended. chromans give favorable results.

In order to improve the storage stability of cyan images, especially the light fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination. This UV absorber may be co-emulsified with the cyan coupler.

The amount of ultraviolet absorber applied should be sufficient to impart photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, it is usually preferable to use lXl0” mol/
It is set in the range of 1.5 x 10-' mol/bo, particularly 5 x 10-' mol/pol.

In the light-sensitive material layer structure of ordinary color paper, a single layer of light on both sides adjacent to a red-sensitive emulsion layer containing a cyan coupler,
Preferably, both layers contain an ultraviolet absorber.

When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent of any particle size.

In the photosensitive material used in the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The photosensitive material used in the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as irradiation or antihalation. Oxonol-based, anthraquinone-based, or azo-based dyes are preferred. Oxonol dyes that absorb green and red light are particularly preferred.

Stilbene-based, triazine-based,
It may also contain a brightening agent such as an oxazole type or a coumarin type. Water-soluble brighteners may be used, and water-insoluble brighteners may be used in the form of dispersions.

The invention is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. Further, each of the above-mentioned emulsion layers may be made up of two or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsion layers having the same photosensitivity.

In addition to the silver halide emulsion layer, the light-sensitive material used in the present invention is preferably provided with auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, and a back layer.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material used in the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

The use of acrylic acid modified polyvinyl alcohol in the protective layer is particularly useful, and even more so when rapidly processed with silver chloride emulsions. In addition to lime-processed gelatin, acid-processed gelatin and Bull gelatin are used.

Soc, Sci, Photo, Japan, , N
Enzyme-treated gelatin as described in J. O., L6+, p. 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

The above-mentioned additives are used in the photosensitive material used in the present invention. These additives are of great importance in rapid printing, rapid processing, and furthermore in relation to the compounds of general formula (I) of the present invention. In addition, especially when the halogen composition of the emulsion to be used contains a high content of silver chloride, the combined use of mercaptoazole, mercaptothiadiazole, and mercaptobenzazole compounds is recommended in order to improve color development and fogging. Useful.

The reflective support j that can be used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. , baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent support with a reflective layer or a reflective material, such as glass plate, polyester film such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
There are polystyrene films and the like, and these supports can be appropriately selected depending on the purpose of use.

(Example) The effects of the present invention will be explained below using Examples.

Example 1 Table A was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper with the layer structure shown below was created. The coating solution was prepared as follows.

First layer coating solution preparation Yellow coupler (a) 19.1g and color image stabilizer (b)
) 4.4g of ethyl acetate 27.2mj2 and solvent (c)
7.9 mf was added and dissolved, and this solution was emulsified and dispersed in 185 ml of a 10% aqueous gelatin solution containing 8 mf of 10% sodium dodecylbenzenesulfonate. - A force-field silver bromide emulsion (containing 1 mol % of silver bromide, 70 g/kg of Ag) was coated with the following venereal sensitizing dye at a rate of 5.0 x 10 per mol of silver chlorobromide.
90 g of a blue-sensitive emulsion was prepared by adding -' moles.

The emulsified dispersion and the emulsion were mixed and melted, and the gelatin concentration was adjusted to have the composition shown in Table A to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution.

The gelatin hardening agent for each layer is 1-oxy-3,5-
Dichloro-8-triazine sodium salt was used.

The following spectral enhancers were used for each emulsion.

Blue-sensitive emulsion layer Green-sensitive emulsion layer (4.0×10-' mole added per mole of silver halide)
Red Sensitive Emulsion Layer The following dyes were used as irradiation prevention dyes in each emulsion layer.

The structural formulas of the compounds used in this example, such as the coupler in the green-sensitive emulsion layer and the red-sensitive emulsion layer, are as follows.

(a) Yellow coupler rθ (C) Solvent (d) Color mixing inhibitor I (f) Color image stabilizer (→ 2:1 mixture of solvent (weight ratio) (h) l:5:3 mixture of ultraviolet absorber ( Molar ratio) (i) Color mixing inhibitor (j) Solvent (iso CJ++*0+T-P = 0(k)
1:1 mixture of cyan coupler (mole ratio) (1) 1:3:3 mixture of color image stabilizer (mole ratio) The obtained color photographic paper was subjected to the following processing steps in which the composition of the color developer was changed. Processed.

Processing process if One-plate color development 35°C 45 seconds bleach fixing 35°C 45 seconds rinse 1
35℃ 20 seconds rinse 2 35℃
Rinse 3 for 20 seconds Dry for 20 seconds at 35°C Rinse for 60 seconds at 80°C was a 3-tank countercurrent water wash from Rinse 3 to Rinse 1. The processing solutions used are as follows.

Additives for left-standing liquids See Table 1 Benzyl alcohol See Table 1 Diethylene glycol See Table 1 Sodium sulfite
0.2g potassium carbonate
30 g EDTA・2Na 1 g Sodium chloride 1.5 g Color developing agent (see Table 1) 0.012 mol Brightener (4,4'-diaminostilbene type) 3.0 g Add water
1000* Ilp H10,0
5 Reduction n constant I cucumber EDTAFe (nl) NH, -2Hz0 60gE
DTA・2Na・2H! 0 4g ammonium thiosulfate (70%) 120sj! Sodium sulfite 16g glacial acetic acid
Add 7g water 1
000m lp H5,5 Yu2su sprinkling formalin (37%) 0.1sj!
l-Hydroxyethylidene-1,l-diphosphonic acid (60%) 1.6sffi
Bismuth chloride 0.35g Aqueous ammonia (26%) 2.5a+ffi nitrilotriacetic acid 3 Na 1. OgED
TA・4H0.5g Sodium sulfite 1.0g5-chloro-2-methyl-4-50rsgIsothiazoline-3
- Addition of on-water LOOOm 11 Two types of color developing solutions were used for each composition: immediately after preparation (fresh solution) and after preparation and left at 35° C. for 21 days (aged solution).

Table 1 shows the photographic properties of the obtained fresh solution and aged solution.

Photographic properties were expressed in three points: Dain, DraX, and gradation at magenta density.

Since Dsin represents the minimum density, Dmax represents the maximum density, and the gradation represents density 0.5, j! It is expressed as a density change up to a density point on the high exposure side of 0.3 ogE.

**Additive (1) NHZNHCONHNHz 1st
As is clear from the table, when hydroxylamine was added, the fog in the aged solution was high and the gradation change was large.

Furthermore, carbohydrazides are not preferred because they cause a large change in Dmax.

On the other hand, it can be seen that when the treatment liquid of the present invention was used, there was little fog and the change in gradation was small even with the aged liquid. Moreover, this effect is particularly pronounced when processed with a developer that does not contain benzyl alcohol.

Example 2 In Example 1, the bromide ion content of the green-sensitive layer emulsion was changed to 8.
When the change in photographic properties of the solution over time was evaluated in the same manner as in Example 1 using 0 mol %, good results were obtained with the configuration of the present invention, with little increase in fog.

Example 3 The first layer (bottom layer) to the seventh layer (
A sample was prepared by applying N) on the layer, and the above-mentioned 1M coating liquid was prepared as follows. yellow coupler 200
g, 93°3g of anti-fading agent, 10g of high boiling point solvent (p) and 5g of (q), and 600rr of ethyl acetate as an auxiliary solvent.
After heating and melting the mixture to 60°C, a 5% gelatin aqueous solution 3 containing 330 ml of a 5% aqueous solution of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) was added.
300 rrl and emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off under reduced pressure from this dispersion, and the sensitizing dye for the blue-sensitive emulsion layer and 1-methyl-2-mercapto-5-acetylamino-1,3,4
- 1400 g emulsion with triazole (9 as Ag)
6.7g, containing 170g of gelatin), and further added 1.
A coating solution was prepared by adding 2,600 g of 0% gelatin aqueous solution. The coating liquids for the second layer to the seventh layer were prepared according to 1N.

Table B The following sensitizing dyes were used in each emulsion layer.

Premalignant emulsion layer; anhydro-5-methoxy-5'-methyl-3,3'-disulfobrovir selenacyanine hydroxide green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3 '-Disulfoethyloxacarbocyanin, 'Roxide red-sensitive emulsion layer, 3.3'-diethyl-5-methoxy-9
, 9''-(2,2-dimethyl-1,3-propano)thiadicarpocyanine iodide.The following substances were also used as stabilizers for each emulsion layer.

1-Methyl-2-mercapto-5-acetylamino-1
, 3,4-) The following were used as lyazole and irradiation-preventing dyes.

4-(3-carboxy-5-hydroxy-4-(3-(
3-Carboxy-5-oxo-1-(4-sulfonatophenyl)-2-pyrazolin-4-ylidene)-1-propenyl)-1-pyrazolyl)benzenesulfonate-dipotassium salt N,N'-(4, 8-dihydroxy-9,10-dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt and 1,2-bis(vinylsulfonyl)ethane as a hardening agent. was used.

The couplers used are as follows.

yellow coupler magenta coupler The cyan coupler was changed as shown in Table 2.

The compounds used in this example are as follows.

UV absorber (n): 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole UV absorber (0): 2-(2-hydroxy-3,5-di-tert-butyl Phenyl)benzotriazole solvent (p) Nidi(2-ethylhexyl) phthalate solvent (q) Nidibutyl phthalate antifade agent (r): 2,5-di-tert-amylphenyl-3,5-di-tert-butylhydroxybenzoate Color mixing inhibitor (S): 2.5-Di-tert-octylhydroquinone Anti-fading agent (M): 1.4-Di-tert-amyl-2,5-dioctyloxybenzene Anti-fading agent (U): 2.2'- methylenebis-(4-methyl-6-tert
-Butylphenol The multilayer color photographic paper obtained above was subjected to wedge-shaped exposure and then processed in the following processing steps.

About 1 minute vLJiL Temperature color development 3 minutes 30 seconds 33°C bleach fixing 1 minute 3
0 seconds 33°C Rinse (3 tanks, 2 minutes 30°C cascade) Drying 1 minute 80″C The processing solution used is as follows.

Sadan Second Son Statue Liquid Water 800m
ff1 triethanolamine 10
mjl! 5.6-cyhydroxy-1.2.4-benzenetrisulfonate sodium 300gN,
N'-bis(2-hydroxybenzyl)ethylenediamine-N.

N'-Diacetic acid 0.1g Nitrilo-N,N,N-)rimethylenephosphonic acid (40%) 1.0g Potassium bromide 0.6g Additives
Table 2 Sodium sulfite Table 2 Potassium carbonate
30g N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbene type) 1.0g Add water 1000mJ! KOH
&, :te pH10, 10th base I
Namisen Osulfate Ammonium (70%) 150mj
! Sodium sulfite 15g Ethylenediamine iron (■) Ammonium 60g Ethylenediaminetetraacetic acid 10g Fluorescent brightener (
4,4'-diaminostilbene type) 1.0g2-
Add mercapto-5-amino-3,4-thiadiazole 1.0g water to 1000mj! With ammonia water pH 7, OIJ 7 solution 5-chloro-2-methyl-4-isothiazolin-3-one 40mg2-methyl-4-isothiazolin-3-one 10mg2-
Octyl-4-inchazolin-3-one 10mg Bismuth chloride (40%) 0.5g Nitrilo-N,N,N-trimethylenephosphonic acid (40%) 1.0g1-
Hydroxyethylidene-1,1-diphosphonic acid (60%) 2.5g Fluorescent brightener (4,4'-diaminostilbene type) 1.0g ammonia water (26%) Add 2.0ml water 1000n+j! K.O.
For each composition, pH 7.5 color developer was tested immediately after preparation (fresh solution) and after 1 hour at 38°C after preparation (aged solution).
type was used.

The Dmin, Dmax, and gradation of cyan were determined for the fresh solution and the aged solution, and the differences between the results obtained for the aged solution and the fresh solution are shown in Table 2.

*: Cyan coupler A H Cyan coupler BO It can be seen that there is little change in Moreover, this effect is more remarkable when the sulfite ion concentration in the treatment liquid is lower.

On the other hand, when processing with a processing liquid to which hydroxylamine is added, there is a large increase in fog and a large change in gradation as the color developer ages.

Furthermore, when a photosensitive material containing a cyan coupler represented by general formula (C-I) is processed with the processing solution of the present invention, a photosensitive material containing a cyan coupler other than general formula (C-1) is processed. It can be seen that there is less increase in fog over time of the color developer and less change in gradation than in the case where the color developer is used. Moreover, this effect is more remarkable when the sulfite ion concentration in the treatment liquid is lower.

Example 4 Using the color photographic paper obtained in Example 1, a running test was conducted in the following processing steps until the tank capacity (60 g) of the color developer was refilled three times.

However, the composition of the color developer was changed as shown in Table 3.

Processing temperature Temperature Time Replenishment One-shot color development 35°C 45 seconds 160me/rt (Bleach fixing 35°C 45 seconds 100m It/rd Rinse■ 30℃ 20 seconds - Rinse■ 3
0°C 20 seconds - Rinse 30°C 20 seconds
200II11! ,/Po Drying 60 to 70°C for 30 seconds The rinsing was performed using a 3-tank countercurrent force type from Rinse (1) to Rinse (2).

The composition of each treatment liquid used is as follows.

Sadan Nihiki Image Solution L Eku Solution Capture Solution Triethanolamine 8.0g 10
．． 0g Additive See Table 3 Fluorescent brightener (4,4'-diaminostilbene type) 3.0g 4
．． 0g ethylenediaminetetraacetic acid 1.0g
1.5g potassium carbonate 30
．． 0g 30.0gEZE solution Replenishment solution Sodium chloride 1.4g 0
．． 1g 4-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido)ethyl)-aniline sulfate 5.0g 7.0
g Benzyl alcohol See Table 3 Diethylene glycol See Table 3 5-Methyl-7-hydroxy- 3,4-triazaindolizine 30 mg -
Add water 1000m 1 10
00m 12p H10,1010,50 Bleach 'Methane and EDTAFe (
I[[)NH4・2Hz0 60 gEDTA
・2Na ・2Hz0 4 g Sodium thiosulfate (70%) 120 mj2 Sodium sulfite 16 g Glacial acetic acid
Add 7g water
1000ml 1 pH 5.5 Rinse Methane and ' is 6g E DTA ・2 Na ・2 HzO Add 0.4g water and 1000mA! pl (7,0) Processed using the above processing method, and measured the B (blue), G (green), and R (red) densities of the unexposed areas at the start and end of running using a Fuji self-recording densitometer. Furthermore, the sample at the end of the run was rotated at 60°.
After being left under C170%RH for two months, the B, G, and R densities of the unexposed areas were measured again.

The results obtained are shown in Table 3.

From Table 3, when hydroxylamine is added,
It can be seen that while the increase in fog after running is large, when the processing liquid of the present invention is used, the increase in fog after running is small and the increase in stain over time after processing is also suppressed. This effect is particularly noticeable when running with a processing solution that does not contain benzyl alcohol.

Example 5 A multilayer photographic paper 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.

(Preparation of first layer coating solution) Yellow coupler (ExY-1) and (ExY-2)
10.2g, 9.1g and color image stabilizer (Cpd-
1) 27°2 cc of ethyl acetate and a high boiling point solvent (So 1v-1) to 4.4 g 7. 7 cc (8.0 g) was added and dissolved, and this solution was mixed with 185 ml of a 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.
It was emulsified and dispersed in cc.

This emulsified dispersion and emulsions EM, 1, and EM2 were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the -Nth layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-5-) riazine sodium salt was used.

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

(Layer structure) The composition of each layer is shown below. The number is coating N (g/rrf
) represents. The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOz) and a bluish dye. ] Nth (blue-sensitive layer) Monodisperse silver chlorobromide emulsion (EMI) spectrally sensitized with an enhancing dye (ExS-1) Monodisperse silver chlorobromide emulsion (EMI) spectrally sensitized with a 0.13 sensitizing dye (ExS-1) Dispersed silver chlorobromide emulsion (EM2) 0.13 Gelatin 1.86 Yellow coupler (ExY-1) 0.44 Yellow coupler (E
xY-2) 0.39 color image stabilizer (Cpd-1)
0.19 Solvent (Solv-1) 0.
35 Second layer (color mixture prevention layer) Gelatin 0.99 color mixture prevention agent (Cpd-3) O, O8 tertiary M (green sensitive layer) Monodispersed salt spectrally sensitized with aggravating dye (ExS-2,3) Silver bromide emulsion (EM3) Monodisperse silver chlorobromide emulsion (EM4) spectrally sensitized with 0.05 enhancing dye (ExS-2,3) 0.11 gelatin 1.80 magenta coupler (E'xM-1) ) 0.39 color image stabilizer (Cpd-
4) 0.20 color image stabilizer (Cpd-5)
o, 02 color image stabilizer (Cpd-6)
o, 03 Solvent (Solv-2) 0.12 Solvent (Solv-3) 0.25 Fourth layer (ultraviolet absorption layer) Gelatin 1.60 Ultraviolet absorber (Cpd-7/Cp d-8/Cp d-9 = 3/2/6: Weight ratio) 0.70 Color mixing inhibitor (Cpd-10) 0.05 Solvent (Sol
v-4) 0.27 Fifth layer (red-sensitive layer) Monodisperse silver chlorobromide emulsion (EMS) spectrally sensitized with sensitizing dye (ExS-4,5) 0.07 Enhanced dye (ExS-4) , 5) Monodisperse silver chlorobromide emulsion (EM6) spectrally sensitized with 0.16 gelatin 0.92 cyan coupler (
ExC-1) 0.32 color image stabilizer (Cpd-
8/C pd-9/Cpd-12=3/4/2: weight ratio) 0.17 Dispersing polymer (Cpd-11) 0.28 Solvent (
Solv-2) 0.20 Sixth N (ultraviolet absorbing layer) Gelatin 0.54 Ultraviolet absorber (Cpd-7/Cp d-9/Cp d-12= 115/3: weight ratio) 0.21 Solvent (
Solv-2) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%') 0.17 Liquid paraffin 0.03 Also, at this time, irradiation prevention The dye for use is (Cpd-1
3, Cpd-14) was used.

Furthermore, each layer contains Alkanol
xF 120 (manufactured by Dainippon Ink Co., Ltd.) was used. As a stabilizer for silver halide (cpct-15,16)
was used.

Details of the emulsion used are as follows.

Breasts ■Each abduction punishment 1 fallen 4L (b)■) 1 Toru EM1 1
．． 0 80 0.08EM2 0
．． 75 80 0.07EM3 0
．． 5 83 0.09EM4
0.4 83 0.1 OEM5
0.5 73 0.09EM6
Q, 4 73 G, 10 The structural formula of the compound used is as follows.

xY-1 Same as yellow coupler (a) of Example 1.

xM-1 CJ+t(t) xC-1 xS-1 5OsHN(CzHs)a xS-2 xS-3 xS-4 Same as the spectral sensitizer for the red-sensitive emulsion layer in Example 1.

ExS-5 Cpd-1 Same as color image stabilizer (b) in Example 1.

Cpd-2 +cut-C)(+-r Ma S　O,K Cpd-3 p d-4 Same as color image stabilizer (f) in Example 1.

p d-5 Ct H% Cpd-6 Otsu H + r (t) Cpd-7 pa-a Cpd-9 Cpd-10 Same as color mixing inhibitor (i) of Example 1.

Cpd-11 Cpd-12 Solv-1 Dibutyl phthalate 5olv-2) Lycresyl phosphate 5olv-3 Trioctyl phosphate 5olv-4) Linonyl phosphate Cpd-13 Cpd-14 Cpd-15 Cpd-16 Imagewise exposure of the above sample After that, the composition of the color developer was changed and continuous processing was carried out in each of the following processing steps until twice the tank capacity of the color developer was replenished.

Processing process Temperature LJ Compensation capacity Color development 38°C 1 minute 40 seconds 290mff1
17ffi bleach fixing 33°C 60 seconds 150m
l 91Wash ■ 30~34°C 20 seconds -
41 water wash■ 30~34°C 20 seconds -41 water
Wash ■ 30-34℃ 20 seconds 200ml
4 j2 Drying 70 to 80°C for 50 seconds *per 1M of photosensitive material (3 tank countercurrent system from water washing to ■) The composition of each processing solution is as follows.

Left Puni developer 2 Ekutatsu replenishment water
800d 800sf Diethylenetriaminepentaacetic acid 1.0g 1.0g Nitrilotriacetic acid 2.0g 2.0g 1-Hydroxyethyrythene-1,1-diphosphonic acid 2.0g 2.0g Potassium bromide 0.5g - Potassium carbonate
30g 30gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.5g 7.5g Additives (Table 4) 0.04mol 0.06mo
l Fluorescent brightener (WRITEX4B manufactured by Sumitomo Chemical) 1.5 g 2.0 g Triethylenediamine (1,4-diazabicyclo(2,2,2) octane) 5.0 g 5.0 g
Add water 1000if 1000
dPH (25°C) 10.20 10.
60 thick pages fixed base liquid Eh 7? wave capture liquid water
400rall 400
mfl ammonium 1000 sulfate (70%) 200mf 300
++1 Sodium sulfite 20g 40
g Ethylenediaminetetraacetic acid iron (III) ammonylum 60 g 120 g
Disodium ethylene diamine acetate 5g Add 10g water to make 1000#lJ! 1000 relative pH (25℃) 6.70 6.30 Water running water (tank liquid and replenisher are the same) Ion exchange water (calcium, magnesium each 3 ppm or less) In each running liquid obtained as above , the above photosensitive material is processed, Dmin immediately after processing and 6 after processing.
Table 4 shows the measured values of Dmin after 11 months at 0° C. and 170% RH.

From the results in Table 4, it can be seen that according to the present invention, stibine was improved not only immediately after treatment but also over time after treatment.

Example 6 A multilayer color photosensitive material having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

89th layer Protective layer B8 layer Ultraviolet absorption layer B7 layer Blue-sensitive emulsion layer No. 86 Ultraviolet absorption layer B5 layer Yellow filter layer E4 layer
Ultraviolet absorbing layer 83rd layer Green-sensitive emulsion layer E2N Ultraviolet absorbing layer B1 layer Red emulsion layer support layer B1 Anti-curling layer B2 layer The protective layer coating solution was prepared as follows.

Preparation of E1 layer coating solution 13.4 g of cyan coupler (ExCC-1), 5.7 g of color image stabilizer (ExSA-1) and polymer (Ex
P-1) 10.7g, 40cc of ethyl acetate and solvent (
ExS-1) 7.7cc was added and dissolved, and this solution was
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of sodium dodecylbenzenesulfonate. A unidirectional latent image type emulsion (containing 63'g/kg of Ag) was mixed with the red-sensitive sensitizing dye shown below at 2.5X1 per mole of silver.
A 0-' mole addition was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare an E1 layer coating solution having the composition shown below.

The coating solutions for the 89th layer and the 81st and 82nd layers from E2BJ were also prepared in the same manner as the EIN coating solution. l-oxy-3,5-dichloro-5-) riazine sodium salt was used as the gelatin hardening agent for each layer.

The following spectral sensitizing dyes were used in each layer.

Red-sensitive emulsion layer: (3.1X10-' mol per 111 mol of halokenide)
Blue-sensitive emulsion layer: (4.3 x 10-' mol per 1 mol of halogenated emulsion)
The following dyes were used as anti-irradiation dyes.

Anti-irradiation dye for green-sensitive emulsion layer Anti-irradiation dye for red-sensitive emulsion layer Same as the anti-irradiation dye for red-sensitive emulsion layer in Example 1.

(Layer structure) The composition of each layer is shown below. The numbers represent the amount of coating per hole. Silver halide emulsion and colloidal silver represent coating amounts in terms of silver.

Support polyethylene laminate paper [The polyethylene on the E1 layer side contains a white pigment (TiO□) and a bluish dye (ulmarine blue)] No. EIF! Silver halide emulsion 0.39g gelatin 1.35g cyan coupler (
ExCC-1) 0.40g color image stabilizer (ExS
A-1) 0.17g polymer (ExP-1)
0.32g solvent (ExS-1)
0.23g development regulator (ExGC-1)
321ng stabilizer (ExA-1) 5.8 m
g Nucleating accelerator (ExZS-1) 0.37 mg Nucleating agent (ExZK-1) 9.9 μg E2 layer gelatin 1.6 g Ultraviolet absorber (ExtJV-1) 0.62 g Color mixing inhibitor (
ExKB-1) 0.06g solvent (Ex
S-2) 0.24g E3 layer silver halide emulsion 0.27g gelatin 1.79g magenta coupler (ExMC-1) 0.32g color image stabilizer (ExSA-
2) 0.20g solvent (ExS-3)
0.65g development regulator (ExC; C-1)
22mg stabilizer (ExA-1) 4mg nucleation accelerator (ExZS-1) 0.26mg nucleation agent (ExZK-1) 3.4μg E4 layer gelatin 0.53g ultraviolet absorber (ExUV-1) O,, 21g color mixing prevention agent
(ExKB-2) 0.02g solvent (E
xS-2) 0.08g E5 layer colloidal silver 0.10g gelatin 0.53g ultraviolet absorber (
F, xUV-1) 0.21g color mixing inhibitor (Ex
KB-2) 0.02g solvent (ExS-
2) 0.08g E6N 87th layer silver halide emulsion same as E4 layer 0.26g gelatin 1.83g yellow coupler (ExYC-1) 0.83g color image stabilizer (ExSA-
3) 0.19g2 volume (ExS-
4) 0. 35g development regulator (ExG
C-1) 32mg stabilizer (ExA-1)
2.9 mg Nucleation accelerator (ExZS-1) 0.
2 ■ Nucleating agent (ExZK-1) 2.5ag No. E8
Layered gelatin 0.53g Ultraviolet absorber (ExUV-1) 0.21g Medium
(ExS-2) 0. 08g No. E
9-layer gelatin 1. 33g Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17g Liquid paraffin 0.03g Latex particles of polymethyl methacrylate (average particle size 2.8 μm) 0. 05 No. 81
Layered gelatin 8.7 g Section B2
The structural formula of the same compound used in the Jl E9 layer is as follows.

(ExCC-1) Cyan coupler (ExMC-1) Magenta coupler (ExYC-1) Yellow coupler (ExSA-1) Color image stabilizer CHlCHgCOOCaHtt CaH*(t) CnH*(t) 5:8:9 mixture (weight ratio) of (ExSA-2) Color image stabilizer Same as color image stabilizer (f) in Example 1.

(ExSA-3) Color image stabilizer Same as color image stabilizer (b) in Example 1.

(ExUV-1) Ultraviolet absorber CHz CH! COOCs HI? C4Hq(t) C4He(t) 2:928 mixture (weight ratio) (ExKB-1) Color mixing prevention agent (ExKB-2) Color mixing prevention agent Same as color mixing inhibitor (d) in Example 1.

(ExGC-1) Development regulator (ExA-1) Stabilizer 4-hydroxy-6-methyl-1,3,3a.

7-Titrazaindene (ExZS-1) Nucleating agent 2-(3-dimethylaminopropylthio)-5-mercapto-1,3,4-thiadiazole hydrochloride (ExZK-1) Nucleating agent 6-nitoxythiocarponyl Amino-2-methyl-1-
Propargyl quinolinium trifluoromethanesulfonate (ExP-1) polymer -÷cH*-CH); i- CONHC, Hq(t) Average molecular weight so, oo.

(ExS-1) Solvent (ExS-2) Solvent Same as solvent (j) in Example 1.

(ExS-3) Solvent 2:1 mixture (by volume) of (ExS-4) Solvent Same as solvent (C) in Example 1.

After the above photosensitive material was imagewise exposed, the composition of the color developer was changed and running processing was performed in the following processing steps.

゛Processing process iJf:! ! ! Replenishment amount "d color development 38°C 1 minute 40 seconds 300mf 10!
.

Bleach fixing 33°C 60 seconds 300ml 5
1Wash ■ 30~34°C 20 seconds -21Wash ■
30-34°C 20 seconds 300m 1 21 Drying 70-80°C 50 seconds *Per photosensitive material (3 tanks countercurrent force type from water washing → ■) The composition of each processing solution is as follows. .

Satan Niri image liquid Eze Etatsu replenishment liquid water
800mff1 800dl-Hydroxyethylidene-1,1-diphosphonic acid 2.0g 2.0g
Ethylenediamine-N.

N,N',N' -tetramethylenephosphonic acid 1.5g 1.5g potassium bromide 1.5g -potassium carbonate
30g 30gN-ethyl-N-(
β-Methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.5g 7.5g Additives (Table 5) 0.05mol 0.07m
ol triethanolamine 10.0 g 10
．． 0 g optical brightener (WRITEX4B ゛-4-sodic acid
1.5 2.0 Add water
1000rn11000rn11000°C)
10.20 10.60 Bakio fixer
Replenishment liquid Replenishment liquid water
400 relatives 400mfl ammonium thiosulfate (70%) 200d 300d
Sodium sulfite 20g 40g Ethylenediaminetetraacetic acid iron(III) ammonium 60g 120
g 1 ium sodium acetate ethylene diamine 510 Add water 1000d 1000d
pH (25°C) 6.70 6.3
0 water (tank fluid and refill fluid are the same) Ion exchange water (3 ppm each of calcium and magnesium
Below) This sample was treated with each running liquid in the same manner as in Example 5, and the Dmin was measured, and the results are shown in Table 5.

From the results in Table 5, according to the present invention, not only Dmin is low, but also the increase in staining over time after treatment is small.

(Effects of the Invention) According to the present invention, the stability of the developer is significantly improved, and as a result, even in the processing method using the developer after aging, an increase in capri and gradation changes are significantly suppressed, resulting in excellent photographs. An image with characteristics was obtained.

Such effects of the present invention were particularly remarkable in color developing solutions that do not substantially contain benzyl alcohol, which has a high pollution load.

Furthermore, the effects of the present invention were more pronounced when the sulfite ion concentration in the treatment liquid was lower. Furthermore, the effects of the present invention were remarkable when processing light-sensitive materials containing specific cyan couplers.

Claims (2)

[Claims] (1) Processing of a silver halide photographic light-sensitive material characterized by processing the silver halide photographic light-sensitive material after exposure with a developer containing at least one kind of hydrazide represented by the following general formula (I). Method. General formula (I) R^1-X-NHNH-R^2 (wherein, ^1 represents a hydroxyl group, hydroxyamino group, carbamoyl group, hydrazinocarbonyl group, amino group, or hydrazino group, R^2 is a hydrogen atom, an alkyl group,
Or represents an aryl group. A dimer or more multimer may be formed by the substituents R^1 and R^2. However, when X is -CO-, R^1 does not become a hydrazino group. ) (2) The method for processing a silver halide photographic material according to claim (1), wherein the developer substantially does not contain benzyl alcohol.