JPH04124662A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the processing method for a silver halide color photographic sensitive material which allows rapid processing, has an excellent liquid preservable property and processing stability and can attain the decrease of pollution by using a stabilizer which contains a hexamethylene tetramine compd. and specific compds. and does not contain formalin. CONSTITUTION:The silver halide color photographic sensitive material is subjected to imagewise exposing then to color development processing and processing with a bleach-fixing bath followed by processing with a stabilizer. The stabilizer which does not substantially contain the formalin and contains the hexamethylene tetramine compd. and at least one kind of the compds. selected from the compds. expressed by general formulas [F-1] to [F-10] is used as this stabilizer. These compds. are made to exist stably in the stabilizer by maintaining the pH of the stabilizer at >=7.5.

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 more specifically, the present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically, a method for processing silver halide color photographic materials, which enables rapid processing, and has good storage stability and processing stability. The present invention relates to a method for processing silver halide color photographic materials which is excellent and can further reduce pollution.

[Conventional technology]

In general, in silver halide photographic materials, a dye image is formed by a series of photographic processes whose basic steps are a color development step and a desilvering step after image exposure.

In the color development step, the oxidized form of the color developing agent undergoes a coupling reaction with the coexisting color coupler, thereby forming a dye image of one image pattern and simultaneously producing reduced silver.

In two successive desilvering steps, the silver produced here is oxidized by a bleaching agent, transformed into a soluble silver complex by the action of a fixing agent, and dissolved and removed by washing with water.

In automatic developing machines having such a developing process, waterless washing technology has been introduced in recent years, bringing benefits such as no maintenance required, processing simplification, speed, and convenience due to reduced installation space. For this reason, there is a tendency to rapidly spread and expand the market for such automatic processors and minilabs.

However, with the introduction of automatic processing in the minilab market, new problems have arisen, including scratches on color negative films due to sticking phenomena and jamming during film transport.

In particular, it has been found that when a stabilization treatment is performed directly after treatment with a fixer as a treatment process, the hardness and f phenomena appear conspicuously. In addition, in the case of a process in which stabilization treatment is performed directly after treatment with a bleach-fix solution, the problem may be relatively minor, or if treated with a stabilizer containing formalin, the problem may be caused by the sticking phenomenon in the stabilizer. understood.

However, in order to solve these problems, if the stabilizer is free of formalin, there are problems such as a decrease in the storage stability of the dye image, a decrease in the concentration of the macenta dye, and the occurrence of yellow stain.

On the other hand, techniques using formalin substitute compounds are also known. That is, in JP-A-63-244036 and JP-A-2-1.53348, hexamethylenetetramine compounds, hisxahytrotriacin compounds, and N
- Used as a methylol compound or a substitute for formalin. The use of such a formalin substitute compound is expected to improve the storage stability of the stabilizing solution and to be effective against the sticking phenomenon.

However, the above-mentioned formalin replacement compound technology is
The inventors' studies have revealed that there are the following problems. Namely, (1) the effect on fixation may decrease due to differences in the amount of treatment and during long-term treatment, and in some cases, the storage stability of the solution may decrease; (2) the presence of pre-bath components, especially high concentrations of thiosulfate in the pre-bath; It has been found that there is a limit to the effectiveness of fixing solutions containing

(Problems to be Solved by the Invention) Therefore, the purpose of the present invention is, firstly, to provide a processing method that enables rapid processing and does not cause scratches due to sticking, and secondly, it has excellent liquid storage stability and is stable. Thirdly, it is an object of the present invention to provide a processing method that makes it possible to substantially remove formalin and achieve low pollution.

[Means to solve the problem]

In order to achieve the above purpose, the inventors of the tree made the following results after intensive study.
This led to the present invention.

That is, 1. The method for processing a silver halide color photographic light-sensitive material according to the present invention is to subject the silver halide color photographic light-sensitive material to imagewise exposure, one color development treatment, and then to process it with a bleach-fix solution.
In a method for processing a silver halide color photographic light-sensitive material, which is then processed with a stabilizing solution, the stabilizing solution does not substantially contain formalin, and contains a hexamethylenetetramine compound and the following - Shipbuilding [F-1] It is characterized by containing at least one compound selected from the compounds represented by ~[F-10] (hereinafter referred to as the compound of the present invention if necessary), and having a pH of 7.5 or more. shall be.

general formula [11 [In the formula, R] ~R6 is Each hydrogen atom or monovalent Represents an organic group.

] general formula [31 %formula% general formula [F-4] [During the ceremony.

R7 represents a water lI:jf atom or a methylol group,] General formula [5] [wherein, Vl and Wl represent an electron-withdrawing group, and
Vl and Wl may be combined to form a 5- or 6-membered nitrogen-containing heterocycle, Yl represents a hydrogen atom or a group that is eliminated by hydrolysis, Z represents a nitrogen atom and a) C=O group together Represents a group of nonmetallic atoms necessary to form a monocyclic or condensed nitrogen-containing heterocycle] General formula [F-7] [In the formula, R8 represents a hydrogen atom or an aliphatic group, and R9 and Rho each represent represents an aliphatic group or an aryl group, R9 and R
ho may combine with each other to form a ring, Zl and Z
2 each represents an oxygen atom, a negative sulfur atom, or -N(R++)-, provided that 21 and 22 simultaneously represent an oxygen atom or -)l(
RH)-.

R1+ represents a hydrogen atom, a hydroxy group, an aliphatic group, or an aryl group.] General formula [F-8] General formula [F-9] Wz-0(-(:H20+nY2 -Funzo [F-10] [Formula where RI2 represents a hydrogen atom or an aliphatic hydrocarbon group, V2 represents a group that is eliminated by hydrolysis, M represents a cation, and W2 and Y2 each represent a hydrogen atom or a group that is eliminated by hydrolysis. , n represents an integer of 1-10, Z3 represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a group that is eliminated by hydrolysis, RI3 represents an aliphatic hydrocarbon group or an aryl group, Z3 represents may be combined with RH to form a ring.] In addition, in the method for processing a silver halide color photographic light-sensitive material according to the present invention, a hexamethylene compound is contained in the stabilizing solution as shown below - Shipbuilding [A-1] It is characterized by being a compound represented by or a salt thereof.

-Ship stock [A-1] Aco [In the formula, AI''A4 represents a hydrogen atom, an alkyl group, an alkenyl group, or a pyridyl group, i represents O or 1] Furthermore, as a preferred embodiment of the present invention, , the amount of coated silver in the silver halide color photographic light-sensitive material is 5.0 or less per silver halide color photographic light-sensitive material [1], and at least 0.0. 1 mol/l, and the replenishment amount of the bleach-fixing solution is 800 m or less per 1 m'' of silver halide color photographic light-sensitive material.

(Effect) The present inventors investigated the causes of differences in processing amounts, a decrease in the effect on fixation during long-term treatment, and in some cases a decrease in liquid storage stability, and found that there was a large change in p)l of the stabilizing solution. It was found that the above problem could be solved by setting the pH of the stabilizing solution to 7.5 or more and using a bleach-fixing solution instead of a fixing solution as a pre-bath of the stabilizing bath, and the present invention. This is what led to this. Further, at the above pH value, when the stabilizing liquid contains at least one compound selected from hexamethylenetetramine compounds and the compounds represented by the above-Funazura [F-11 to [F-10],
We have discovered the completely unexpected fact that these compounds exist stably and exhibit the effects of the present invention, leading to the present invention.

[Specific structure of the invention]

Preferably, the hexamethylenetetramine compound used in the stabilizing liquid in the present invention is a compound represented by the above-mentioned -Funazo [A-1] or a salt thereof.

In the general formula [A-1], each group represented by Al-A4 includes a substituent, such as a carbamoyl group, a halogen atom such as a chlorine atom, or an aryl group such as a phenyl group.

Examples include hydroxyl group, carboxyl group, and oxycarbonyl group such as methoxycarbonyl group.

The alkyl group represented by A1-A4 has 1 to 1 carbon atoms.
Those having 5 carbon chains are preferred.

- Salts of the compound shown in ship stock [A-1] include inorganic acid salts such as hydrochlorides, sulfates, and nitrates, organic acid salts such as phenol salts, double salts or complex salts with metal salts, and hydrated salts. Examples include inner salts.

- Specifically, the compound shown in [A-1] in Shipyard is Peilsteins: Handbuch der e Organie/
Die-Hemi (Beilstein Handbu)
ch dar Organishan Chemie)
(7) Compounds described in RII Jll Supplementary Edition Vol. 26, pages 200-212 can be mentioned. Among them, those soluble in water are preferred in the present invention.

Representative examples of the compound represented by the general formula [A-1] or the salt of Seven are listed below.

-f-1 J-5 A-1-18 CI.

Although the compound of general formula [A-x] is easily available as a commercially available product, it can also be easily synthesized using the method described in the above-mentioned literature.

- The compounds in shipyard [A-1] may be used alone or in combination of two or more, and the amount added is 0.1 g per 1 treatment liquid.
A range of ~20g is preferred.

Next, the general formula [F-1] to be used in the present invention [F-1]
-10] will be explained.

In the general formula [F-1], RI-R6 each represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, and an aralkyl group. , an amine group, an alkoxy group, a hydroxy group, an acyl group, a sulfonyl group, an alkylthio group, an arylthio group, a heterocyclic residue, a carbamoyl group, a sulfamoyl group, or an argylamino group.

These -valent organic groups have substituents (e.g., hydroxy group, acyl group, sulfonyl group, halogen atom, amino group,
Examples include a carboxy group, and preferably a hydroxy group or a halogen atom. or,
The total carbon number of the substituents represented by R1 to R6 is preferably 10 or less.

The group R+, R3, Rs and the group R2, Rs, Rb may be the same or different, but it is preferable that one of the groups is all hydrogen atoms.

Specific examples of the compound represented by the general formula [F-1] are shown below, but the invention is not limited thereto.

F-1-1 CII□CIl, O1+ C11゜ F-1-4 C11, - CIl Tomi C11゜ -1-s +11fflIl1I-oIl SO,I+ il ■ ell, CIICIIs F-1-10 CIl, CIl, CII, NIL ω-CIl-CFI.

F-1-14 OCI+.

(N) Cll s ONVM 侃1゜CI(,011 These triazine compounds represented by -Funezo [F-1] are preferably used in an amount of 0.05 to 50 g per stabilizer. , more preferably O, 1g to 20
g range.

- Ship Stock Specific examples of the methylol compound represented by [F-2], [F-3] or [F-4] include the following compounds.

(F-2-1) Dimethylol urea (F-2-2) ) Dimethylol urea (F-3-1)
Dimethylolguanidine (F-4-1) ) Limethylolmelamine (F-4-2) Tetramethylolmelamine (F-4-3) Pentamethylolmelamine (F-4-4) The amount of hexamethylolmelamine added is based on the stabilizing solution. 1! 0.05~20. is preferable, more preferably 0.1 to 1 Og/1, and within this range, the effects of the present invention can be effectively achieved.

In [F-5] and [F-6], the electron-withdrawing values indicated by Vl and Wl are determined by Hammett's ffp value (Lange'a Handbook of C
hemistry 12th ed, Vol. 3. C,
Hansch & A, Leo, 5ubsLituen
tCon5LanLs for Correl
ation Ana17sisin Chemis
try and Biolog7 (Jane W.
ile7 & 5ons.

New York 197'l)) is positive, specifically acyl groups (eg, acetyl, benzoyl, monochloroacetyl, etc.), alkoxycarbonyl groups (eg, ethoxycarbonyl).

methoxyethoxycarbonyl, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl, p-chlorophenoxycarbonyl, etc.), carbamoyl groups (e.g.,
H-methylcarbamoyl, N, totitramethylenecarbamoyl, N-phenylcarbamoyl, etc.), cyano group, alkylsulfonyl group (e.g., methanesulfonyl, ethanesulfonyl, etc.), arylsulfonyl group (e.g., benzenesulfonyl, p-toluenesulfonyl, etc.) ), sulfamoyl groups (eg, sulfamoyl, tomethylsulfamoyl, N,N-pentamethylenesulfamoyl, etc.).

The group shown by Yl that leaves by hydrolysis is:
For example, trialkyl-substituted silyl groups (e.g., trimethylsilyl, etc.), acyl groups (e.g., acetyl, benzoyl, etc.),
monochloroacetyl, trifluoroacetyl), sulfate group, ami7 carbonyl group (e.g., N, N
-dimethylcarbonyl, H-methylcarbonyl, etc.), sulfonate groups (e.g. methanesulfonate,
benzenesulfone), p-)luenesulfonate, etc.)
Examples include groups such as

The 5- or 6-membered nitrogen-containing heterocycle formed with the nitrogen atom represented by 2 and the C═O group is [CI84]
, [02N! ] , IC3N21 , [C4N]
, [C2N41.

[C3Nx], [CsNz], [:sN]
, [G2N20], [CxNO].

[C3NzO], [:sNO]. [C2N2S].
[CxNS1. [G3NTe1.

[(zN2sel, [C3NSa], [04N
Monocycles consisting of elemental compositions such as Sel, [G3NTe1, [03Hz-Cil, [CiH-(61.

[CiH-CIN 21 , (C 3N re3N
21, (C3)Fi-Cil, (CsM-C
sM].

[CsN-C61, [CiH2-C61, etc.], and on these rings, for example, alkyl groups (e.g., methyl, ethyl, methoxyethyl, benzyl, carboxymethyl4 sulfopropyl, etc.) , aryl group (e.g., phenyl, p-methoxyphenyl, etc.), hydroxy group, alkoxy group (e.g., methoxy, ethoxy, methoxyethoxy, etc.), aryloxy group (e.g., phenoxy, p-carboxyphenyl, etc.), carboxy group, sulfonate group, alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl, etc.), amine group (e.g., N, N-dimethylamino, N-ethylamino, tophenylamino, etc.) ,
Acylamide group (e.g., acetamide, benzamide, etc.), carbamoyl group (e.g., carbamoylmethylenecarbamoyl, etc.), sulfonamide group (e.g., methanesulfonamide, benzenesulfonamide, etc.)
, sulfamoyl groups (e.g., toethylsulfamoyl, N,N-dimethylsulfamoyl, etc.), alkylsulfonyl groups (e.g., methanesulfonyl, ethanesulfonyl, etc.), arylsulfonyl groups (e.g., benzenesulfonyl, p-toluenesulfonyl, etc.) etc.), acyl groups (eg, acetyl, benzoyl, etc.), and the like.

In the general formula [F-5], the 5- or 6-membered nitrogen-containing heterocycle that can be formed via the divalent electron-withdrawing groups 1 and W] is the following general formula [F-5]. -5-a
Examples include those shown by l.

General formula [F-5-al In general formula [F-5-al, ■1 and W+ are each h
-GO-, -Go-0-, -So-, -SOz or -CS- group, Zl is bonded to ■1 and W+ to form 51
Or represents a group of nonmetallic atoms necessary to form a 6-membered monocyclic ring or fused ring.

Any ! on the 5- or 6-membered monocyclic or condensed ring formed by Zl! It can have an l substituent! .

Examples of such arbitrary groups include alkyl groups (e.g., methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.), aryl groups (e.g., phenyl, p-methoxyphenyl, etc.), hydroxy groups, and alkoxy groups. (e.g. methoxy, ethoxy, methoxyethoxy, etc.), aryloxy groups (e.g. phenoxy, P
-carboxyphenyl, etc.), carboxy group, sulfo group,
Alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl, etc.), amino groups (e.g., N.trimethylsilyl, H-ethylamino, N-
phenylamino, etc.), acylamido groups (e.g., acetamide, benzamide, etc.), carbamoyl groups (e.g.,
carbamoyl N-methylcarbamoyl, N,N-tetramethylenecarbamoyl, etc.), sulfonamide group (e.g. methanesulfonamide, benzenesulfonamide, etc.) 2-sulfamoyl group (e.g. toethylsulfamoyl.N, todimethylsulfamoyl) etc.), alkylsulfonyl groups (eg, methanesulfonyl, ethanesulfonyl, etc.), arylsulfonyl groups (eg, benzenesulfonyl, P4 luenesulfonyl, etc.), acyl groups (eg, acetyl, benzoyl, etc.), and the like.

Specific examples of the compounds represented by the general formulas [F-5] and [F-81 used in the present invention are shown below, but the invention is not limited thereto.

The amount of the compound represented by the general formula [F-5] or [F-61 to be added is preferably 0.01 to 20 g, more preferably 0.03 to 15 g, and particularly preferably 0.03 to 15 g per stabilizer. 0.05
~IOg.

Said - Shipbuilding [In F-73, Ra, u 9 and R
The aliphatic group represented by io includes a saturated alkyl group (
For example, unsubstituted alkyl groups such as methyl, ethyl 2-butyl, substituted alkyl groups such as benzyl, carboxymethyl, hydroxymethyl, methoxyethyl, etc.), unsaturated alkyl groups (for example, allyl, 2-butenyl, etc.),
Examples include cyclic alkyl groups (domestic lf, cyclopentyl, cyclohexyl, etc.).

The aryl groups represented by R*, RIo, and R include substituted and unsubstituted ones, and examples of substituents include alkyl groups (e.g., methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.) , aryl group (e.g., phenyl, p-methoxyphenyl, etc.) 2
Hydroxy group, alkoxy group (e.g., methoxy, ethoxy, methoxyethoxy, etc.), aryloxy group (e.g., phenoxy, p-carboxyphenyl, etc.), carboxy group, sulfo group, alkoxycarbonyl group (e.g.,
methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl 21i (e.g., 2-phenoxycarbonyl, etc.), ami7 group (e.g., NJI-dimethylamino, N-ethylamine, tophenylamino, etc.), acylamide group (e.g., acetamide, benzamide, etc.), carbamoyl groups (e.g., carbamoyl, H-methylcarbamoyl, N,N-tetramethylenecarbamoyl, etc.),
Sulfonamide groups (e.g. 1, methanesulfonamide).

benzenesulfonamide, etc.), sulfamoyl groups (e.g., toethylsulfamoyl, N,N-dimethylsulfamoyl, etc.), alkylsulfonyl groups (e.g., methanesulfonyl, ethanesulfonyl, etc.), arylsulfonyl groups (e.g., benzenesulfonyl), , P-)luenesulfonyl, etc.), acyl groups (eg, acetyl, benzoyl, etc.), and the like.

The ring formed by bonding R9 and RIG includes a 5- to 8-membered heterocycle, including one in which a portion of the bonded carbon atoms are substituted with other biplane atoms.

R8 is preferably a hydrogen atom.

Specific examples of the compound represented by the general formula [F-7] used in the present invention are shown below, but the invention is not limited to these compounds.

CI, OH tHi C11,011 - The amount of the compound shown in shipyard [F-7] is stabilized solution 1
0.01 to 20 g per 1 is preferable, more preferably 0.01 to 20 g per 1
．． 0.03 to 15 g, particularly preferably 0.05 to 1 h.

R12 in the above-ship storage [F-83 to [F-10],
As the aliphatic hydrocarbon group represented by R13 and z3,
Saturated alkyl groups (e.g. methyl.

unsubstituted alkyl groups such as ethyl, butyl, substituted alkyl groups such as carboxymethyl, methoxymethyl, methoxyethylhydroxyethyl, benzyl, etc.), unsaturated alkyl groups (e.g. allyl, 2-butenyl, etc.), cyclic alkyl groups ( Examples include cyclopentyl, cyclohexyl, etc.). The aryl groups represented by R13 and z3 may be substituted, and substituents include, for example, alkyl groups (
Methyl, ethyl, methoxyethyl, benzyl.

carboxymethyl, sulfopropyl, etc.), aryl group (
For example, phenyl, p-methoxyphenyl, etc.), hydroxy group, alkoxy group (for example, methoxy, ethoxy,
methoxyethoxy, etc.), aryloxy groups (e.g., phenoxy, p-carboxyphenyl, etc.), carboxy groups, sulfo groups, alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), aryloxy groups (e.g., phenoxycarbonyl, etc.) ),
Ami7 group (e.g. 2N, trimethylsilyl).

N-ethylamino, tophenylamino, etc.), acylamide X (e.g., acetamide, benzamide, etc.), carbamoyl'X (e.g., carbamoyl.

N-methylcarbamoyl, NN-tetramethylenecarbamoyl, etc.), sulfonamide groups (e.g., methanesulfonamide, benzenesulfonamide, etc.), sulfamoyl groups (e.g., H-ethylsulfamoyl, N,N-diethylsulfamoyl, etc.) ).

Alkylsulfonyl groups (e.g., methanesulfonyl, ethanesulfonyl, etc.), arylsulfonyl groups (e.g.,
Examples include any group selected from groups such as benzenesulfonyl, p-)luenesulfonyl, etc.), acyl groups (eg, acetyl, benzoyl, etc.), and the like.

vt, w2. Examples of the groups represented by y2 and Z3 that are eliminated by hydrolysis include acyl groups (e.g.
acetyl, benzoyl, trifluoroacetyl, monochloroacetyl, etc.), trialkylsilyl groups (eg, trimethylsilyl, etc.), and the like.

The ring formed by combining RH with 23 is a 5-8 negative saturated ring or a condensed ring, and also includes a ring in which a part of the bonded carbon chain is substituted with other heteroatoms.

Specific examples include rings such as 1,2-dioxacyclopentane, dioxane, trioxane, tetraoxane, and benzdioxolane.

Examples of the cation represented by M include hydrogen ions, alkali metal ions (for example, ions such as lithium, sodium, and potassium), alkaline earth metal ions (for example, ions such as magnesium and calcium), ammonium ions, and organic ammonium ions. Examples include ions (for example, ammonium ions such as triethylammonium, tripropylammonium, and tetramethylammonium), pyridinium ions, and the like.

The aliphatic hydrocarbon group represented by the general formula [F-8] to [F-101 C2R12 is preferably a lower alkyl group having 1 or 2 carbon atoms, and it is generally preferred that R12 is a hydrogen atom. More preferred.

Specific examples of the compounds represented by -Funzo [F-8] to [F-101] are shown below, but the present invention is not limited to these compounds.

F-8-1 P-8-2 C11,C00(CHffiO)3COCII.

Cll3COO(CH*O) tcOclIsCB,C
00 (CIl, O), COCl+.

[0(CH,O),,+1 CeCHICOO(CH2O), C0CHtCI2-I
Q-1 F・1O-2 P-10-21 The amount of the compound represented by the general formula [F-8], [F-9] or [F-10] is 0.01 to 20 per treatment solution.
g is preferable, more preferably 0.03 to 15.g. .

Particularly preferably 0.05 to IQg.

The replenishment amount of the stabilizing solution is 870 mM or less per rn' of the photosensitive material, preferably 5001 rn' or less.

In the present invention, the pH of the stabilizing solution is 57.5 or more,
Preferably S, O~1! , 0, more preferably 8.5~
It is 10.5. It was completely unexpected that the compound of the present invention stably exists within this range and exhibits the effects of the present invention significantly. The pH adjuster that can be contained in the stabilizing solution may be any commonly known alkaline agent or acid agent.

In the present invention, the stabilizing solution preferably contains a chelating agent having a chelate stability constant of 8 or more for iron ions, where the chelate stability constants are L, G, 5.
illan* A, 1E-Kartell, -5ta
bi1ity Con5tants of Me
tal-ion ComplexegTbaCbem
ical 5ociety, London (1984
), S, Chab@rek * A, E, Mart
Written by @ll, ” Organic Sequsgtsr
ingAgentj'', W+Iey (+858), etc.

Examples of the chelating agent having a chelate stability constant of 8 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Note that the above-mentioned iron ion means ferric ion (Fe3').

Specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include, but are not limited to, the following compounds: ethylenediamine diorthohydroxyphenylacetic acid, Diaminopropane tetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediamineniprobionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid , glycol ether diamine tetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonethane-2-carboxylic acid, 2-
Phosphonobutane-1,2,4-)licarboxylic acid, l-hydroxy-1-phosphonopropane-1,2,3-)licarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate.

Examples include sodium tetrapolyphosphate and sodium hexametaphosphate, and particularly preferred are diethylenetriaminepentaacetic acid 2nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,l-diphosphonic acid, and 1-hydroxyethylidene-1,1-diphosphonic acid. 1,1
-diphosphonic acid is most preferably used.

The amount of the above chelating agent used is 0.01 to 5 per 11 of the stabilizer.
0 g is preferred, and more preferably 0.05 to 20, good results can be obtained.

Also, examples of compounds that can be added to the stabilizing solution include ammonium compounds. These are supplied by ammonium salts of various inorganic compounds, including ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, and fluoride. Ammonium, acidic ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium bicarbonate, ammonium bifluoride, ammonium bisulfate, ammonium sulfate, ammonium iodide.

Ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, ammonium lauric tricarboxylate, ammonium benezoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, Ammonium phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ammonium ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate,
Ammonium phthalate.

Ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4.
6-dolinitrophenolammonium and the like. These may be used alone or in combination of two or more. The amount of the ammonium compound added is preferably in the range of o.ooi mol to 1.0 mol, more preferably 0.002 to 2.0 mol, per 11 of the stabilizer.
It is in the range of 0 mol.

Furthermore, the stabilizing solution may contain sulfite.

If the sulfite releases sulfite ions,
Any organic or inorganic substance may be used, but inorganic salts are preferred. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, and hydrosulfide. The above sulfite is present in the stabilizing solution at least 1
It is preferable to add in an amount such that the amount becomes
It is added in an amount such that the amount is 1 mole/cross, and is particularly effective in preventing stains. Although it may be added directly to the stabilizing solution, it is preferable to add it to the stable replenisher.

The stabilizing liquid may contain a metal salt in combination with the chelating agent. Such metal salts include Ba, Ca,
Ca, Go, In, La, M! l, old, Bi,
Pb, Sn.

Zn, Ti, Zr, Kg, AJL or Sr metal salts are available, and can be supplied as sa salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates, or water-soluble chelating agents. The amount to be used is 1 serving of stabilizer IX.
The range is preferably from 10-4 to IX 10-1 mol, more preferably from 4X 10-4 to 2X 10-2 mol.

Organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH3L adjusters (phosphates, borates, hydrochloric acid, sulfates, etc.), etc. may be added to the stabilizing solution. can. These compounds may be added in any combination of amounts that are necessary to maintain the PL+ of the stabilizing bath and do not adversely affect the stability of color photographic images during storage and the occurrence of precipitation. do not have.

Note that in the present invention, known fungicides can be used.

The stabilizing liquid may contain a surfactant.

Further, as the surfactant, a silicone compound represented by the following general formula is preferable because it has the effect of preventing sticking in addition to the conventionally known effect of preventing water droplet unevenness and defoaming.

CHx Here, a, b, d, e are integers from 5 to 30, and C is from 2 to 5.
and R is an alkyl group having 3 to 6 carbon atoms.

Further, it is preferable to add an alkanolamine to the stabilizing solution in order to prevent sulfurization of thiosulfate ions introduced by the photosensitive material. The use of alkanolamine is described in US Pat. No. 4,785,583.

In the process of the present invention, silver may be recovered from the stabilizing solution.
In addition, the stabilizing solution can be treated with ion exchange treatment, electrodialysis treatment (see Japanese Patent Application No. 59-96352!@) and reverse osmosis treatment (Japanese Patent Application No. 59-96352!@).
-96532), and it is also preferable to use water that has been deionized in advance, i.e., the anti-fungal properties of the stabilizing solution, the stability of the stabilizing solution, and the image storage properties. This is because improvements can be made. As a means of deionization treatment, 5p of Ca and Mg ions are added to the rinse water after treatment.
Any material may be used as long as it reduces the temperature to pm or less, but
For example, ion exchange resins and reverse osmosis membranes, which are preferably treated alone or in combination, are described in detail in Kokai Technical Report No. 87-1984.

The salt concentration in the stabilizing solution is 11,000 ppm or less, preferably 2, more preferably 800 ppm or less.

Note that a soluble iron salt may be present in the stabilizing solution.

The treatment temperature during the stabilization treatment is preferably in the range of 15°C to 70"C, more preferably in the range of 20°C to 55°C. Also, the treatment time is preferably 120 seconds or less, more preferably 3 seconds. ~90 seconds, most preferably 6 seconds to 50 seconds.

The stabilization tank is preferably composed of a plurality of paddles, preferably 2 to 6 tanks, particularly preferably 2 to 3 tanks, even more preferably 3 tanks, and a counter current system (after bath). It is preferable to use a method in which the water is supplied and overflowed from the pre-bath.

After the stabilization treatment, no water rinsing treatment is required, but rinsing with a small amount of water in a very short time, surface cleaning, etc. can be optionally performed as necessary.

Color developing agents used in the color development process include:
Although there are amine phenol compounds and p-phenylene diamine compounds, p-phenylene diamine compounds having a water-soluble group are preferred in the present invention.

Such a water-soluble group has at least one on the 7-mino group or benzene nucleus of the p-phenylenediamine-based compound, and the specific water-soluble group is as follows.

-(CH2)*-CH2OH1 -(GHz)s- to H! 902-(CH2) n-CH
z, -(GHz)s-0-(C:Hz) n-CHx,
-(CHzCH20)ncJ2s◆+ (m and n each represent an integer of 0 or more, ), -COOH group, -
Preferred examples include 5O3H group.

Specific examples of color developing agents preferably used in the present invention are shown below.

Margin below [Example color developing agent] (A-1) Cuffs Ctll-NIISO*Cll5\/ to N.H.

(A-2) 0.1.N10.11.08 Nil.

(A-3) 0・II・N10・1・011 811° (A-4) 0 mountain\10.11.0011. (A C, II, C, Il, SO, I+\/ N11° (A-6) 01(・N10・1″・Oll N.H.

(A-7) HO84C* Cd140ft \/ Nl+! (A-8) 0.(1.N10.11.80°11 Among the color developing agents exemplified above, examples No. 1, (A-1), (A-2), ( ^-
3), (A-4), (A-8), (^-7) and (A-
This is the compound shown in 15).

The amount of color developing agent added is 0.5 per 1 color developer.
It is preferable that Xl0-2 mol or more, more preferably 1.0 X IQ-2 to 1. Q X 10-'MoJ
1.5 Xl0, most preferably 1.5
-2~? , OXl0-2 moles.

The color developing agents mentioned above are usually used in the form of salts such as hydrochloride, sulfate, and ρ-toluenesulfonate.

What color developer is used in the color development process?

It may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. Furthermore, various additives such as benzyl alcohol, alkali halides such as potassium bromide or potassium chloride, or development! 11 As a setting agent, for example, citradinic acid, etc. As a preservative, hydroxylamine, hydroxylamine rust conductor (
For example, diethylhydroxylamine), hydrazine derivatives (eg, hydrazine derivatives), sulfites, and the like.

Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide, and dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developer is usually 7 or higher, preferably about 9.
~13.

The color developer may optionally contain tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic@2flucol, hydroxamic acid, pentose or he-r-sose, pyrogallol-1, as an antifusing agent. 3-dimethyl ether and the like may also be contained.

Used as a sequestrant for metal ions in color developing solutions.

Various chelating agents can be used in combination 6 For example, the chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, organic phosphonic acids such as l-hydroxyethylidene-1,1-diphosphonic acid, aminotri(methylene phosphonic acid) or 7-minopolyphosphonic acid such as ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid,
Examples include phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-)licarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and the like.

The preferred replenishment amount of the color developer in continuous processing is preferably 150Osii or less, more preferably 250Osii or less per 1ITI' of the light-sensitive material for color negative films.
It is 0 to 800 cm, more preferably 300 to 700 cm.

The bleaching agent used in the bleach-fix solution in the present invention is as follows-
The ferric complex salt of the organic acid represented by Shipura (A) or [B] and the second exemplified compound shown by A'-1-18 etc. below
Examples include iron complex salts.

- Ship storage (A) [In the formula, A + "A s may be the same or different, -CHzOH, 000% or -Po 3N I
Represents N2.

M, N+, and N2 each represent a hydrogen atom, an alkali metal, or ammonium; X represents a substituted or unsubstituted fullkylene group having 3 to 6 carbon atoms; General formula (B) is the same as defined in -Funakura (A) above, n represents an integer from 1 to 8, and B1 and B2 may be the same or different, and each has 2 carbon atoms.
-5 represents a substituted or unsubstituted fullkylene group] The compound represented by the general formula (A) will be described in detail below.

A1-A4 may be the same or different, and -C
H20) 1, -〇〇〇〇 or -P03MIM2,
X, Ml, Ml each represent a hydrogen atom, an alkali metal (e.g. sodium, ram) or ammonia,
X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (e.g. propylene, butylene, pentamethylene, etc.),
Examples of the substituent include a hydroxyl group and a furkyl group having 1 to 3 carbon atoms.

Preferred specific examples of the compounds shown in (A) above are shown below.

(A-1,) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7) (A-8) (A-9) (A-10 ) (A-11) (A-12) These compounds (A-1) to (A-12)! As the ferric complex salt, sodium salt, potassium salt or ammonium salt of these ferric complex salts can be arbitrarily used6.
From the viewpoint of the desired effect and solubility of the present invention, ammonium salts of these ferric complex salts are preferably used.

Next, the compound represented by the general formula CB) will be explained in detail.

Al to Todoroki 4 have the same meanings as above, n represents an integer of 1 to 8, and B1 and B2 may be the same or different.

Substituted and unsubstituted Alkylev MC each having 2 to 5 carbon atoms
f14yt4f ethylene, propylene, butylene, pentamethylene, etc.), and examples of the substituent include a hydroxyl group and a lower alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, propyl group).

Preferred specific examples of the compound represented by -Funazou CB) are shown below.

(B-1) (B-2) (B-3) (B-4) CB-5) (B-6) (B-7) These compounds (B-1) to (B-7) As the ferric complex salt, a sodium salt, a potassium salt, or an ammonium salt of a ferric complex salt of these compounds can be arbitrarily used.
In the present invention, since the oxidizing power of the bleaching agent is sufficiently high and bleach fog is likely to occur in the case of ammonium salt, the ammonium salt is preferably 50 mol% or less, preferably 2.
A preferred embodiment of the present invention is 0 mol % or less, particularly preferably 10 mol % or less.

In the bleach-fix solution, preferable bleaching agents other than the compounds shown in (A) or (B) above include ferric complex salts of the following compounds (e.g. salts of ammonium, sodium, potassium, triethanolamine, etc.). Examples include, but are not limited to.

(A'-1) (A'-2) (A'-3) (A'-4) Ethylenediaminetetraacetic acid trans-1,2-cyclohexanediaminetetraacetic acid dihydroxyethylglycinate ethylenediaminetetrakismethylenephosphonic acid (A'- 5) Nitrilotrismethylenephosphonic acid [A
'-6] Diethylenetriaminepentakismethylenephosphonic acid [A'-7] Diethylenetriaminepentaacetic acid (A'-8
) Ethylenediaminediorthohydroxyphenylacetic acid [A'-9] Hydroxyethylethylenediaminetriacetic acid [＾'-10) Ethylenediaminedipropionic acid (
A'-11) Ethylenediamine diacetic acid (A'-12
) Hydroxyethyliminodiacetic acid (A'-13)
Nidosolotriacetic acid (A'-14) Nitrilotripropionic acid (^'-
15) Triethylenetetraminehexaacetic acid (A'-16
) Ethylenediaminetetrapropionic acid Bleaching agents preferably used in the present invention include (A-1), (A
-3), (A'-1), (A'-2), and (A'-7) organic acid ferric salts.

The amount of organic acid ferric complex salt added is 0.1 per 11 parts of the bleach-fix solution.
The content is preferably in the range of mol to 2.0 mol, more preferably 0.15 to 1.5 mol/cross.

In the present invention, the above bleaching agent may be used alone,
You may use two or more types in combination.

Organic acid iron (m) complex salts may be used in the form of complex salts, and iron (m) salts such as ferric sulfate, ferric chloride, ferric acetate, ferric ammonium sulfate, ferric phosphate, etc. An iron (m) ion complex salt may be formed in a solution using diiron, etc. and aminopolycarboxylic acid or its salt, or when used in the form of a complex salt, one type of complex salt may be used. In addition, two or more types of complex salts may be used. Furthermore, when forming a complex salt in a solution using a ferric salt and an aminopolycarboxylic acid, a ferric salt and an aminopolycarboxylic acid may be used.
One or two types of iron salt! I1 or more may be used, and aminopolycarboxylic acids of Ill or 2@ or more may be used, and in any case, aminopolycarboxylic acids may be used to form iron (m) ion complex salts or more. May be used in excess.

Further, the bleach-fix solution containing the above-mentioned iron (m) ion complex may also contain metal ion complex salts other than iron, such as cobalt, copper, nickel, and zinc.

The bleach-fix solution may contain a bleach accelerator.

As the bleaching accelerator used in the present invention, US Pat.
3,693.1158, German Patent 1g 1,
290.812, British Patent No. 1.1.38,8
Specification No. 42.

Compounds having a mercapto group or disulfide group described in JP-A-53-95630 and Research Disclosure No. 17129 (July 1978 issue) Thiazoline derivatives described in JP-A-50-140129, U.S. Patent No. Thiourea conductors described in the specification of JP-A No. 3,706,561, iodides described in JP-A-58-16235, polyethylene oxides described in the specification of German Patent No. 2,748,430, 45-811:1
Polyamine compounds described in Japanese Patent No. 6 can be used. Particularly preferably British Patent No. 1.138,842
Preferred are mercapto compounds such as those described in No.

The amount of bleach accelerator added is 90.01 g per 1 quart of bleach-fix solution.
20 g, preferably 0.1 g to log.

When adding a bleaching accelerator, it may be added and dissolved as is, but it is common to dissolve it in water, alkali, organic acid, etc. before adding it, and add methanol, ethanol, acetone, etc. as necessary. It can also be added after being dissolved in an organic solvent.

In an embodiment of the present invention, it is preferred that the bleach-fix solution used in the present invention contains thiocyanate as a fixing agent.

It is preferable that the thiocyanate is contained in an amount of 0.1 mol or more per bleach-fix solution, more preferably 0.3 mol/i.
Above, particularly preferably 0.5 mol/a~3.0 mol/l
It is. The use of thiocyanate not only has an effect on fixing properties, but also has the effect of improving the storage stability of the stabilizing solution itself.

In addition to these fixatives, it also contains various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. p
One or more H* buffers may be included.

Furthermore, it is desirable to contain a large amount of a rehalogenating agent such as an alkali halide or an ammonium halide, such as potassium bromide, sodium bromide, and ammonium sodium chloride. Compounds known to be added to fixers can be added as appropriate.

Silver may be recovered from the bleach-fix solution by known methods, such as electrolysis method (described in Buddhist Patent No. 2,211!1,8117), precipitation method (described in JP-A-52-73037, Germany). (described in Japanese Patent No. 2,331,220), ion exchange method (described in Japanese Unexamined Patent Publication No. 17114/1982, National Patent No. 2,5411,237), and metal substitution method (described in British Patent No. 1,353, 805 specification) etc. can be used for emotions.

It is particularly preferable to recover silver from the tank solution in-line using an electrolytic method or an anion-exchange resin, as this improves suitability for rapid processing, but it is also possible to recover silver from the overflow waste solution and reuse it. .

The amount of replenishment of the bleach-fixing solution is preferably 800 μm or less per rn' of the light-sensitive material, and more preferably 150 to 7001 layers per rn' of the light-sensitive material. Within this range, the effects of the present invention are noticeable.

For the bleach-fixing solution, Japanese Patent Application No. 83-48931 Specification No. 5
A compound represented by the general formula [FA] described on page 6 and exemplified compounds thereof may be added, and another effect can be obtained in that sludge generated when a small amount of light-sensitive material is processed over a long period of time is extremely small.

The compound represented by the general formula [FA] described in the same specification is described in U.S. Patent No. 3,335,181 and U.S. Patent No. 3,28
It can be synthesized by a general method as described in US Pat. No. 0,718. These compounds represented by -Funzo [FA] may be used alone or in combinations of 21Ii or more.

In addition, good results can be obtained when the amount of the compound represented by "Fanzo [FA]" is in the range of Q, 1 g to 200 g per 12 of the treatment liquid.

Sulfites and sulfite-releasing compounds may be used in the bleach-fix solution; specific exemplary compounds include potassium sulfite, sodium sulfite, ammonium sulfite, type ammonium bisulfite, potassium bisulfite, sodium bisulfite, meth Examples include potassium bisulfite, sodium metabisulfite, ammonium metabisulfate, and the like. Further included are compounds represented by the general formula [B-1] or [B-23] described on page BO of Japanese Patent Application No. 83-481131.

These sulfites and sulfite-releasing compounds are present in fixer solution 11.
At least 0.05 mol of sulfite ion is required per sulfite ion, but the range of O, Oa mol/4 to 0.65 mol/cross is preferable, and the range of 0.10 mol/l to 0.50 mol/cross is particularly preferable. , most especially 0.12 mol/i~0
．． A range of 40 mol/IL is preferred.

The temperature of the bleach-fix solution is preferably 80°C or lower, more preferably 30°C to 70°C.

The pH of the bleach-fix solution is preferably 5.0 or higher, more preferably in the range of 6.0 to 9.0.

The pH of the bleach-fix solution is the pn of the processing tank during processing of the silver halide photosensitive material, and can be clearly distinguished from the pH of the so-called replenisher.

The processing time with the bleach-fixing solution according to the present invention is optional or preferably 4 minutes 30 seconds or less, more preferably 10 seconds to 3 minutes 45 seconds, particularly preferably 20 minutes to 3 minutes 15 seconds. It is.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the processing bath and processing replenisher storage tank as desired, or an appropriate oxidizing agent, such as peroxide, may be used. Hydrogen, bromate, persulfate, etc. may be added as appropriate.

In the processing method of the present invention, it is preferred as an embodiment of the present invention that the bleach-fix solution is subjected to forced stirring.
The term "forced liquid stirring" as used herein means adding a stirring means to forcibly stir the liquid, rather than the normal diffusion and movement of the liquid.

A specific method of forced stirring is disclosed in Japanese Patent Application Laid-Open No. 1834-1983.
No. 60, No. 62-183461 2 U.S. Patent No. 4,75
8,858, a method of impinging a jet of processing liquid on the emulsion surface of a light-sensitive material, and JP-A-62-183461.
A method of increasing the stirring effect using a rotating means, a method of improving the stirring effect by creating turbulence on the emulsion surface with a wiper blade installed in the liquid, and a method of increasing the circulation flow rate of the entire processing liquid. can give.

It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate.

Further, the agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the accelerator results and eliminate the bleaching accelerator's effect of inhibiting bleaching.

In addition, in the present invention, a cross-over time of each calibration from a color developer tank to a bleach-fix tank, etc. within 10 seconds, preferably within 7 seconds is effective against bleach fog, which is a different effect from the present invention. Furthermore, a method of installing a duck hill valve or the like to reduce the amount of processing liquid brought in by the photosensitive material is also a preferred embodiment of the present invention.

Silver halide color photographic material (hereinafter referred to as “
The silver halide grains used in the "photosensitive material" or "r-sensitive material" may be any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Silver bromide is preferably used.

The amount of coated silver in the silver halide color photographic light-sensitive material is preferably 5.0 per rn' of the silver halide color photographic light-sensitive material.
In other words, the average silver iodide content of all the silver halide emulsions in the halogenated light-sensitive material having a silver amount in the above range is 0.1 g or less, preferably 2.0 to 4.5 g. ~
Preferably 15 mol%, more preferably 0.5 S12
It is mol %, particularly preferably 1 to 10 mol %.

The average grain size of all the silver halide emulsions in the light-sensitive material is preferably 2.0 to 1 or less, more preferably 0.1 to 1.0 to.

When the silver herodanide emulsion contains grains having an average value of grain size/grain thickness of less than 5, it is preferable from the viewpoint of desilvering properties that the grain size distribution is monodisperse.

A monodisperse silver halide emulsion is a monodisperse silver halide emulsion with ±
The weight of silver halide contained within the 20% grain size range is 80% or more of the total weight of silver halide grains, preferably 70% or more, and more preferably 80% or more.

Here, the average particle size 7 is the frequency n of particles having particle size ri
The product niX of i and ri3 is defined as the grain size ri when ri3 is the maximum (3 significant digits, the smallest digit is 5 to 40
people).

In the case of a spherical silver halide grain, the grain size referred to here means the diameter thereof, and in the case of a grain having a shape other than spherical, the diameter when its projected image is converted into a circular image of the same area.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and measuring the particle diameter on the print or surface type at the time of projection (the number of particles measured is (assumed to be over 1000 indiscriminately).

Particularly preferred highly monodisperse emulsions are those in which the breadth of the distribution defined by the average grain size is 20% or less, more preferably 15% or less.

The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [1,0,0] planes to [1,1,1] planes can be used. Furthermore, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and outside are different. These silver halides may be of the type that forms a latent image primarily on the surface, or of the type that forms a latent image inside the grain, or even tabular.
Silver Rorodide grains (see Japanese Patent Application Laid-open No. 113934/1982 and Japanese Patent Application No. 170070/1982) can also be used.

The silver halide grains may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method.

Alternatively, for example, seed grains may be produced using an acidic method and then grown using an ammonia method, which has a fast growth rate, to grow to a predetermined size.When growing silver halide grains, the pH, pAg, etc. in the reaction vessel may be adjusted. It is preferable to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains under controlled conditions, for example, as described in JP-A-54-48521.

Preparation of silver halide grains is preferably carried out as described above.
In this specification, it is referred to as a silver halide emulsion.

In the present invention, silver halide emulsions that are usually subjected to physical ripening, chemical ripening and spectral sensitization can be used. Additives used in such processes are listed in Research Disclosure (RD) No. 1764.
3 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in light-sensitive materials are also described in the above two research disclosures.

The table below shows the relevant entries. Ta.

addition 1 Chemical sensitizer 26 degree increase agent 3 Spectral sensitizer 2 supersensitizer 4 Brightener 5 Antifoggant and stabilizers 6 light absorber.

Filter Dye UV absorber 7 Stain inhibitor 8 Dye image stabilizer 8 Hardener IO binder 11 Plasticizer, lubricant 12 Developing aid, surfactant 13 Sudatic inhibitor HD 17643 23 pages 23-24 pages 24 pages 24 ~25 pages 25-28 pages 25 right column 25 pages 26 pages 2B page 27 pages 2B-27 pages 27 pages RD 18718 648 pages right column Same as above page 648 right column ~ 648 right column 648 pages right column ~ 648 right column - Page 850 Left column Page 850 Left to right column Page 1151 Left column Same as above Page 850 Right column Same as above Same as above Various color couplers can be used in light-sensitive materials, and specific examples thereof can be found in the Research Disclosure (HD) mentioned above. No. 17843. It is described in the patent described in Section 2-C-C.

As a yellow coupler, for example, U.S. Pat.
No. 3,501, No. 4,022,820, No. 4,3
No. 28,024, No. 4,401,752, Special Publication No. 5
B-10739, British Patent Road No. 1,425,020;
Preferably, those described in No. 1,476.780, No. 1, etc.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred;
No. 0,819, No. 4,351,897, European Patent No. 73,838, U.S. Patent No. 3,01?1,432,
No. 3,725.087, Research Disclosure No. 24220 (June 1984), JP-A-8
No. 0-33552, No. 55-118034, No. 80-
No. 185951, Research Disclosure + -No.
, 24230 (June 1984), Japanese Patent Publication No. 80-43
No. 85θ, No. 81-72238, No. 80-35730
No. 4,500,830, U.S. Patent No. 4,540.
No. 854, No. 4,558,830, WO (PCT)
Particularly preferred are those described in No. 88104795.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4,052.212.
No. 4,148.31118, No. 4,228,
No. 233, No. 4,298,200, No. 2,389
, No. 829, No. 2.801, 171, No. 2.77
No. 2,182, No. 2,883,1126, No. 3,
No. 772,002, No. 3,758,308, No. 4
, No. 334,011, No. 4,327,173, West German Jihyo Publication No. 3,329,728, European Patent No. 121.
3f13A, U.S. Patent No. 3,448,822, U.S. Patent No. 4,333. No. IIH, No. 4,451,55θ2, No. 4,427,787, European Patent No. 161.

Those described in No. 628^ are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure) lo, 17B43.
Section ■-G, U.S. Patent No. 4.1113.870, Japanese Patent Publication No. 57-59413, U.S. Patent No. 004,928
No. 4.138.2511, British Patent Road 1,14
8,388 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include:
U.S. Patent No. 4,3H,237, British Patent No. 2,125
．． No. 570, European patent! No. 98,570, West German patent (published)! Preferred are those described in No. i53,234,533.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820, U.S. Pat.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is 2 previously described HD 17843.
．． Patents listed in Sections ■-F, Japanese Patent Application Laid-open No. 57-15194
No. 4, No. 57-154234, No. 80-184248
Preferred are those described in US Patent No. 4,248.1182.

Couplers that release a nucleating agent or a development accelerator imagewise during development are disclosed in British Patent No. 2.0117,140, British Patent No. 2,131,188, and Japanese Patent Application Laid-open No. 15783/1983.
No. 8, No. 511-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include the competitive couplers described in U.S. Pat. , the multi-equivalent coupler described in JP-A No. 4,310,8111, etc., JP-A-80-185850
Examples thereof include DIR redox compound-releasing couplers described in No. 1, No. 1, and European Patent No. 173,302A, which release couplers that release dyes that fade after separation.

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

Examples of high boiling point solvents used in the oil-in-ice dispersion method are described in U.S. Jihyo No. 2,322,027 and the like.

There is also a method of using a polymer as a coupler dispersion medium (Japanese Patent Publication No. 4B-30494, U.S. Patent No. 3,811).
,! No. 95, West German Patent No. 1,957,487, Special Publication F@
There are various descriptions in No. 1ll-311835.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. In, No. 383, OLS No. 2,541,274 and OLS No. 2. ! It is described in No. i41,230, etc.

Supports for photosensitive materials include polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, baryta paper, polyethylene-coated paper, and transparent supports with one radiation layer of polypropylene synthetic paper. The support 1 may be, for example, a glass plate, or may be any other ordinary transparent support, and these supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and other photographic constituent layers. Also, U.S. Patent No. 2,781.781, U.S. Pat.
It is also possible to use a simultaneous coating method of two or more layers according to the method described in No. 41.8138.

The coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color color negative photographic light-sensitive material, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a green-sensitive silver halide emulsion layer are sequentially applied from the support. .

The arrangement of blue-sensitive silver halide emulsion layers is preferred, and each of these light-sensitive silver halide emulsion layers may consist of two or more layers.

In the light-sensitive material processed in the present invention, it is optional to provide an intermediate layer of an appropriate thickness depending on the purpose, and various layers such as a filter layer, an anti-curl layer, a protective layer, an anti-halation layer, etc. They can be used in appropriate combinations as layers. Binders that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of binders that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included.

In the method for processing a photosensitive material of the present invention, as long as the photosensitive material contains a coupler in the photosensitive material and is processed by the so-called internal development method, color negative film, color paper, color positive film, color for slides, etc. It can be applied to any photosensitive material such as reversal film, color reversal film for movies, color reversal film for TV, and reversal color paper.

[Example] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Unexploded Example 1 The following stabilizing solution was prepared.

(Stabilizing liquid) Surfactant C, 1IH1? + 0-(CH*C)ItO+1゜)I
O, 2g triethanolamine
2. Ogl, 2-benzisothiazolin-3one
0.02g Formalin (37K) or compound of the present invention Fixer or bleach-fixer listed in Table 1 pH 9 as listed in Table 1
0 The compositions of the fixing solution and bleach-fixing solution are as follows.

(Fixer Ammonium thiosulfate 250g Anhydrous sodium bisulfite 20g Sodium metabisulfite 4.0g Disodium ethylenediaminetetraacetate 1.0g Add water to make 11, and use glacial acetic acid and aqueous ammonia to make pl 7.
．． Adjust to 0.

(Bleach-fix solution) Ammonium thiosulfate 200g Ethylenediaminetetraacetic acid ferric ammonium dihydrate 150g Ethylenediaminetetraacetic acid disodium salt 5g Ammonium bromide 50g Summer thorium sulfite
Add 15g of water to make 1, and add ammonia water to 11) 1 to 7.0 II! ! do.

After washing the surface of the Noryl resin (assuming the material of the stabilizer tank) with distilled water, 0.2 liters of the above stabilizer was dropped onto the dried resin surface and stored at 50°C and humidity and 50% RH for 30 days. After that, the surface was wiped off with a paper towel moistened with water, and the condition of the surface was visually observed.

The results are shown in Table 1.

However, the following evaluation criteria were followed for the condition of the surface.

■ There is no adhesion to the surface or any deterioration of the surface.

It sticks slightly to the O surface, but can be removed by rubbing vigorously.

Δ It sticks to the surface and can be removed by rubbing forcefully.

X: It sticks to the surface and one surface is slightly altered.

XX Strongly adheres to the surface, causing significant deterioration of the surface.

As is clear from Table 1, the fixing properties in the stabilizing solution were better when the bleach-fixer was contained than the fixer.

In addition, when formalin is contained, the fixing properties are considerably deteriorated, but the compounds of the present invention, especially F-1-1 and F-9
-6, F-10-4, A-1-1, and especially A-1-1 had excellent effects on adhesion.

Example 2 Stabilizer No. 1-2, 1-4 used in Example 1.

The same evaluation as in Example 1 was performed on the stabilizer solution to which the bleach-fix solution No. 1-15 was added.

However, after the stabilizing solution was stored at room temperature for 3 days, it was treated in the same manner as in Example 1, and the storage period was 45 days.

The results are shown in Table 2.

As is clear from Table 2, when the pH of the stabilizer solution changed, when it contained formalin, there was almost no significant difference due to the change in pH, but when the stabilizer solution contained the compound of the present invention, it had a pH of 7. It can be seen that the effect is remarkable in the range of 5 or more, especially in the range of 8.5 to 10.5.

Example 3 Sample A, which is a multilayer color light-sensitive material, was prepared on a cellulose triacetate film support coated with an undercoat and each layer having the composition shown below.

(Composition of photosensitive layer) The coating amount is expressed in chain Kid units for silver halide and colloidal silver, the amount expressed in g/rrf units for coupler additives and gelatin, and the amount expressed in g/rrf units for sensitizing dyes. is expressed as the number of moles per mol of /\Rorodation #[in the same layer. Note that the symbols indicating additives have the meanings shown below. However, if a substance has multiple effects, one of them is listed as a representative.

Uv: ultraviolet absorber, 5olv: high boiling point organic solvent, Ex
F: dye, ExS: sensitizing dye, ExC nitrogen coupler, ExM: magenta coupler, EXY: yellow coupler, Cpd: Additive 1st FF (antihalation M) black colloidal silver 0. lO gelatin 2.9UV-10,0
3 UV-20,08 UV-30,07 Solv-20,08 ExF-10,01 ExF-20,01 2nd layer (low sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform Agl type 1 sphere equivalent diameter 0.4% m, coefficient of variation of sphere equivalent diameter 37%, plate-like particles, diameter/thickness ratio 3.0) Coated silver amount 0.35 Gelatin 0.8xS-1 2,3X 10- 4 ExS-2 1,4X 10-4 ExS-5 ExS-7 xC-1 xC-2 xC-3 3rd layer (medium aperture red-sensitive emulsion layer) 2.3X 10-4 8, OX 10-4 0 .17 0.03 b,! 3 Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2:1
internal high AgI type.

Equivalent sphere diameter 0J5IL■, coefficient of variation of equivalent sphere diameter 23%, plate-shaped particles, diameter/thickness ratio 2.0) Coated silver amount o, e.

Silver iodobromide emulsion (4 mol % of MugI, 1! base, equivalent ball diameter 0.4 l, coefficient of variation of 1 ball equivalent diameter 30%, plate-like grains, diameter/thickness ratio 3.0) Coating Silver amount 0.1 Gelatin ExS-I ExS-2 ExS-5 ExS-7 xC-I xC-2 1,0 2X to-4 1,2X 10-4 Xl0-4 7X10-' 0.31 Oool xC-3 0, OB 4th layer (high sensitivity red-sensitive emulsion FJ) Silver iodobromide emulsion (AgI 6 mol%, core shell ratio 2:l
internal high Agl type, equivalent sphere diameter 0.74 m, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/thickness ratio 2.5) Coated silver amount 0.7 Gelatin ExS-I ExS-2 ExS-5 ExS-7 xC-I xC-4 olv-I olv-2 Cpd-7 5th layer (middle layer) Gelatin V-4 V-5 0,8 1,6X 10-4 1.8X 10-4 1.8X to-4 X1O-4 0,07 0,05 0,07 0,20 4,8 Sensitive emulsion layer) 0.1 0.08 0.05 Silver iodobromide emulsion (Agl 4 mol%, average -A, ! type, equivalent sphere diameter 0.1, coefficient of variation of equivalent sphere diameter 35%, plate-like) Particles, diameter/thickness ratio 2.0) Coated silver amount 0.15 Gelatin xS-3 xS-4 xS-5 xM-5 Ex M-7 Sensitive emulsion calendar) 0.4 2X 1O-4 7X 10-'lXl0" 0.11 0.03 0.0+ 0.08 0.0■ Silver iodobromide emulsion (Ag 14 mol%, core shell ratio 1:1 internal High AgI type.

Equivalent sphere diameter 0-5 gm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 4.0) Coated silver amount 0.24 Gelatin 0.6E x S
-32X 10-' E x S -47X 1O-4 E x S -51X 10-1 0-4Ex 0.17Ex
M-70,04 Ex Y -80,02 Solv-10,+4 S o I v-40,02 8th layer (highly sensitive green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 9.2 mol%, silver Quantity ratio 3:4
:24 mol%, 0 mol%, 2 mol% from the inside of the multilayer structure particle Agr content of 2
, equivalent sphere diameter 0.7 entanglement 1, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/thickness ratio 1.8) Coated silver amount O,S gelatin O,5ExS-45,
2X101 EX S -51X 1O-4 Ex S -80,3X 10-1 0-4Ex 0.1ExM
-6 xY-8 xC-1 xC-4 olv-1 olv-2 olv-4 pci-7 9th layer (intermediate layer) Gelatin Cpd-1 Polyethyl acrylate latex olv-1 10th layer (overlayer for red-sensitive layer) Effect of 0.03 0.02 0.02 0.01 0.25 0.06 0.01 1X 10-4 0, G O2O3 0.12 0.02 Silver iodobromide emulsion with donor layer (Agl 5.5 Mol%, internal high AgI type with a core-shell ratio of 2:1.

Equivalent sphere diameter 0-7IL Coefficient of variation of equivalent sphere diameter 20%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0.83 Silver iodobromide emulsion (Ag 14 mol%, average - AgI type 2 spheres) Equivalent diameter 0.4 bowl, coefficient of variation of sphere equivalent diameter 3
7%, plate-like particles, diameter/thickness ratio 3.0) Coated silver amount 0.15 Gelatin x S-3 x M-10 olv-1 Eleventh calendar (yellow filter layer) Yellow colloidal silver gelatin Cpd-2 olv-1 Cpd -1 Cpd-6 12th layer (low sensitivity blue-sensitive emulsion layer) 8X 10-4 0.19 0.20 0.06 0.8 0.13 0.13 0.07 0.0G2 0.13 Iodobromide Silver emulsion (gl 4.5 mol%, homogeneous -Ag 1L)
Equivalent sphere diameter: 0.7μ Coefficient of variation of equivalent sphere diameter: 18%, plate-like grains, diameter/thickness ratio: 7.0) Coating amount: 0.25 Silver iodobromide emulsion (Agl: 3 mol%, uniform-Agl type, Equivalent sphere diameter 01gm, coefficient of variation of equivalent sphere diameter 30%, root-like particles, diameter/thickness ratio 7.0) Coated silver amount 0.15 Gelatin 1.8E x S
-69x 10 ExC-10,05 ExC-40,03 ExY-90,14 ExY -110,89 Solv-10,42 13th layer (middle layer) Gelatin 0.7 xY-12 0,20 olv -1 0,34 14th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Agl 10 mol%, internal high Agl type 1
Equivalent sphere diameter 1.0 JLm, coefficient of variation of equivalent sphere diameter 23%, multiple twinned plate-like particles, diameter/thickness ratio 2.5) Coated silver amount 0.4 Gelatin 0.5xS-6 xY-9 E x Y - 11 xC-1 olv-1 15th layer (first protection M) 1x10 0.01 0.20 0.02 0.10 Fine grain silver iodobromide emulsion (Agl 2 mol%).

Uniform-Agl type, equivalent sphere diameter 0.07JL) Coated silver amount 0.
10 Gelatin V-4 V-5 olv-5 pd-5 Polyethyl acrylate latex 18th calendar (second protective layer) 0.8 0.11 0.16 0.02 0.13 0.10 0.09 Fine particle oxide Silver bromide emulsion (Agl 3 mol%, homogeneous Agl
fi, equivalent sphere diameter 0.07 layers) Coated silver amount 0.23 Gelatin 0.55 Polymethyl methacrylate particles (diameter 1.5 layers) 0.2H-I
In addition to the above components, each layer of Q and 17 contains an emulsion stabilizer Cp d -3 (0,
07g/r), surfactant Cpd-4 (0,033/r
n') was added as a coating aid.

V V-2 V-3 V-4 V-5 C4Ha(t) H H 5olv-1 Tricresyl phosphate olv-2 Dibutyl phthalate olv-4 olv-5 Trihexyl phosphate xF-1 N(CsHt, )2 xS -1 xS-2 xS-3 xS-4 xS-5 xS-6 (CL)asOs)14(CtHs)sxS-7 xS-8 ExM-5 Cpd-2 Cpd-5 Cpd-3 H Cpd-4 CH *-Cll SOt CIItCONII
Cl1zCI+, =C1l-SQ, -CIl, C0NI
I-CIl.

After subjecting the thus prepared film sample to live exposure using a camera, a running test was conducted under the following conditions.

(The amount of replenishment is the value per 1 m of photosensitive material.) However, the stabilization process was performed using a two-tank counter current, with the final stabilizing liquid tank being replenished and the overflow flowing into the preceding tank. .

The composition of the color developing solution used is as follows.

Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 3.0g Sodium bromide
1.2g potassium iodide
0.8g hydroxylamine sulfate
2.58 Sodium chloride
0.6g4-amino-3-methyl-N-ethyl-N=(
β-hydroxylethyl) Aniline sulfate fJi 4.8g Diethylenetriaminepentaacetic acid 30g Potassium hydroxide 1.2g Add water to make 11, and use potassium hydroxide or 20% sulfuric acid to make p) 11
Adjust to 0.01.

The composition of the color developer replenisher used is as follows.

Potassium carbonate 40° Sodium hydrogen carbonate 3g Potassium sulfite
7g sodium bromide
0.5g hydroxylamine sulfate
3.184-amino-3-methyltoethyl root (
β-Hydroxylethyl) Aniline sulfate 6.0g Diethylenetriaminepentaacid Acetic acid 3.0g Potassium hydroxide 2g Add water to make 1 mixture, and use potassium hydroxide or 20% sulfuric acid to prepare p)I 10.
Adjust to 12.

The compositions of the bleach-fix solution and bleach-fix replenisher used are as follows.

Bleach-fix solution> Ethylenediaminetetraacetic acid ferric ammonium dihydrate 150° Ethylenediaminetetraacetic acid di-sodium salt 5.0g Sodium sulfite 20g Ammonium thiosulfate (70% solution) 250% ,3,4-thiadiazole-2-thiol)
The pH was adjusted to 7.0 with 0.5 g ammonia water.

Ferric ammonium ethylenediaminetetraacetic acid dihydrate 180g Ethylenediaminetetraacetic acid 2 Sodium salt Sodium sulfite Ammonium periosulfate (70% solution) 5.0g 4g 300 Bleach accelerator (5-amino-1, 3,4-thiadiazole-2-thiol) 4g Adjusted to pH 6.5 with aqueous ammonia.

The stabilization method used and the composition of the replenisher are as follows.

Surfactant C,H,,+0-(CH,Cl120+IoH0,15
g5-chloro-2-methylisothiazolin-3-one 0
．． 02g Formalin (37%) or compound coating of the present invention pH described in 3
The above treatment liquid listed in Table 3, treatment process per day from Monday to Wednesday of the week.
Running treatment was performed for 5 weeks with a cycle of 0.2R, 0.0SR from Thursday to Saturday, and a day off on Sunday. (R is tank capacity (V
Total amount of replenisher (R) R/V = round (R)
Furthermore, the treated solution after treatment was placed in a beaker with an opening area of 20 cm'/l, the temperature was controlled at 38° C. for 12 hours a day, and the solution was stored for 2 weeks while stirring with a stirrer, and the appearance of the solution was observed.

Further, the photographic material after processing was stored for two weeks at 50° C. under 75% R)I, and the change in green transmission density before and after the storage processing was evaluated. The evaluation criteria for liquid storage stability were as follows.

■ There is no occurrence of sediment or suspended matter.

0 A very small amount of sediment and floating matter is observed.

Δ A slight amount of sediment and floating matter is observed.

× Although not a large amount of sediment and suspended matter, it is observed.

XX A large amount of precipitates and floating substances are observed.

The results are shown in Table 3.

Table Green transmission density after storage - Green transmission density before storage As is clear from the table 3, using the compound of the present invention, P
)l s, in the case of a stable solution of o or more, fixing property, liquid storage property,
Although sufficiently satisfactory results were obtained in terms of image storage stability, it can be seen that when formalin was used, although there was no particular problem in image storage stability, the fixing property and liquid storage stability were significantly poor.

Example 4 A multilayer color negative film was prepared as follows.

The amount added in a silver halide photographic light-sensitive material is expressed in grams per ltn' unless otherwise specified, and the amounts of iml halide and colloidal silver are expressed in terms of silver. However, the sensitizing dye is expressed in moles per mole of silver halide of the same calendar.

(Photosensitive material sample) 1st layer: Antihalation black colloidal silver 0.2 UV absorber (UV-1) 0.23 High boiling point solvent (Oi
l-1) 0.18 gelatin
1.4 Second Calendar; First Intermediate Calendar Gelatin 1.3 Third Calendar; Low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion 0.5 (average grain size 0.4 final ■, AgI 2.0 mol%) Sensitizing dye (5D-
1) 1.8XIO-5 (mol/moh silver) sensitizing dye (SD-2) 2.8XIO-' (mol/moh silver)
Sensitizing dye (SD-3) 3.0XIO-4 (mol/[1 moA) Cyan coupler CC-1) 0.50 Colored cyan coupler (CC-1) 0.040D
IR compound (D-1) 0.01DIR compound (D-3) 0.01High boiling point solvent (O
il-1) 0.40 gelatin
1.2 4th Calendar; Medium-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion 0.5 (average grain size 0.7 final s, AgI 8.0 mol%) sensitizing dye (SD-
1) 2. 1X10-5 (mol l silver 1 moh) sensitizing dye (SO-2) 1.1 l
) Sensitizing dye (SD-3) 1.9X10=(mol/@
1moh) Cyan coupler (C-1) 0.2
0 Colored cyan coupler (CG-1) 0.02
7 DIR compound (D-1) 0.01 High clear point solvent (Oil-1) 0.28 Gelatin 0.6 Fifth calendar; High sensitivity red-sensitive emulsion layer Silver iodobromide emulsion 0.8 (average grain size 0.8 Touma, Ag18.0 mol%) sensitizing dye (SD-1
) 1. l]
Sensitizing dye (SD-3) 1.7XlO-4 (mol/1 moh silver) Cyan coupler (C-1) 0.0
5 cyan coupler (C-2) 0.05 colored cyan coupler (CG-1) 0.01DIR
Compound (D-1) 0.01 high boiling point solvent (
Oil-1) 0.10 gelatin
1.2 6th calendar: 2nd intermediate calendar gelatin 0.8 7th layer: low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion 0.6 (average grain size 0.4 gm, Agl 2.0 mol%) sensitized Dye (SD~
4) e, ax+o-5 (7 h/1 moh silver) sensitizing dye (SD-5) 8.2XIO-4 (moA/1 mole silver)
Magenta coupler (M-1) 0.30 magenta coupler (M-2) 0.10 colored magenta coupler (CH-1) 0.04 DIR compound (
D-2) 0.01DIR compound (D-
3) o, o + high boiling point solvent (Oil-2)
0.81 gelatin
1.8 8th layer; medium-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion 0.3 (average grain size 0.7 pots, Agl 8.0 mol%) sensitizing dye (S D
-6) 1.9X 1O-4 (mol/silver 1 mol) sensitizing dye (SD-7) 1.2X 101 (moh/silver 1 mol) sensitizing dye (SD-8) 1.5X 1O-5
(Mos/Silver I Moss) Magenta coupler (M-1)
0.03 magenta coupler (M-2) 0
．． 03 Colored Magenta Coupler (fl:M-1)
0.02DIR compound (D-2) 0.0
i3 High boiling point solvent (Oil-2) 0.3
0 Gelatin 0.8 9th layer;
High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion 0.8 (average grain size 1.0 μgl 8.0 mol%) sensitizing dye (SD-8
) 1.2X101(ts/aleA) sensitizing dye (
50-7) 1. QXlo-' (Mos/Silver I Moss)
Sensitizing dye (SD-8) 3.4XlO-6 (7 l/silver 1 mole) Magenta coupler (M-1) 0.0
5 Magenta coupler (M-3) 0.02 Colored magenta coupler (flJ-1) 0.02 High boiling point solvent (Otl-2) 0.20 Gelatin 1.011410 layers: Yellow filter calendar Yellow colloid color 0.03 Color contamination Inhibitor (SC-1) 0.1 High boiling point solvent (Oi
l-2) 0.13 gelatin
0.7 formalin scavenger (I
s-1) o, os formalin scavenger (HS 11th calendar; low sensitivity blue-sensitive emulsion layer 0.07 sensitizing dye (SD-9) 5.2x 10-' (v
h/1 mole of silver) w Color sensitivity Im (50-10) 1.8
XfO-5 (Mos/#Iv, s) Yellow coupler (Y
-1) 0.35 yellow coupler (Y-2
) 0.20DIR compound (D-1)
0.03 high boiling point solvent (Oil-2)
0.18 Gelatin 1.
3 Formalin scavenger (HS-1) 0.08
12th calendar: Highly sensitive blue-sensitive emulsion layer Silver iodobromide emulsion o, e (average grain size 1.0jL, Agr 8.0 mol%) Sensitizing dye (S
D-9) 1.8X 10-' (ts/silver LEA)
Sensitizing dye (SD-10)? , 9X 1o-5C
eh/1 mole of silver) yellow coupler (Y-1)
0.10 Yellow coupler (Y-2) High boiling point solvent (Oil-2) Gelatin formalin scavenger (MS-1) Formalin scavenger () IS-2) 13th calendar; 1st protective layer fine particle iodobromide Silver emulsion (average particle size 0.08 final Agl 1 mol%) Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) High boiling point solvent (Otl-1) High boiling point solvent (Oil-3) Formalin scavenger - (MS-1) Formalin scavenger - (MS-2) Gelatin 14th layer; 2nd protective layer Alkali-soluble matting agent (average particle size 2 ILa) Polymethyl methacrylate (average particle size 3) 0.05 0. 0?4 1.30 0.05 0.12 0.15 0.07 0.10 0.07 0.07 0.13 0.37 1.3 0.13 0.02 Slip agent (wAX-1) 0 .04 Gelatin 0.6 In addition to the above composition, coating aid 5u-1, dispersion aid 5u-2, viscosity modifier, hardening agent H-1, H-2, stabilizer 5T-1, fogging Inhibitor AF-1゜Mw: 10,000 and Mw:
1,100,000 of 21i AF-2 was added.

The emulsion used in the above sample was a monodisperse emulsion with a low surface silver iodide content, and was optimally sensitized with ginseng sulfur according to a conventional method. Note that the average particle size is expressed as a particle size converted into a cube.

C, I+.

0M-1 i O i1 C ■ il V-1 Cjls(t) V-2 C, 11° AX-1 u-1 u-2 D D-4 D-5 c, Ha C, 11° 5D-7 SD -9 1, L; H+Jsl) U5Ng NmeN. Sea lion. 3 (CIl 2 = Cll5OI CIl 2 ) 1
0T-1 nl+ P ■ P-2 After subjecting the above light-sensitive material to live exposure using a camera, add a bleach-fix solution and a bleach-fix replenisher to the composition shown below, and the replenishment amount to 600 μl/rrf. Evaluation was made using the same treatment liquid and treatment steps as in Example 3, except for the following.

However, the stabilizing liquid and stable replenishing liquid are processed No. 3-3,
3-7, 3-10 and 3-12 were evaluated.

The results are shown in Table 4.

Bleach-fixing and bleach-fixing replenisher> Diethylenetriaminepentaacetic acid ferric ammonium salt 0.35 moh fixing agent (shown in Table 4) 2.0 mol ammonium sulfite (40% solution) 40 ml
Ammonium ethylenediaminetetraacetate 2.0g5-amino-1,3,4-thiadiazole-2-thiol
Add 0.5 g of water to make one layer, and adjust to p87.5 with aqueous ammonia or glacial acetic acid.

As is clear from Table 4, even if the fixing agent in the bleach-fixing solution is changed, when the stabilizing solution contains formalin, the fixing properties and solution storage stability tend to be the same as in Example 3. Although no effect was observed, in the case of the compound of the present invention, by adding thiocyanate, the fixing properties and liquid storage stability were significantly improved, and the image storage stability was also slightly improved. There is a tendency to

Example 5 The same evaluation as in Example 4 was conducted by changing the replenishment amount of the bleach-fix solution as shown in Table 5 in Process Nos. 4-5 and 4-10 of Example 4.

The results are shown in Table 5.

Table: Green transmission density after storage - Green transmission density before storage As shown in Table 5, as the bleach-fix solution is reduced in replenishment, when it contains a stabilizer and formalin, it improves fixation and storage stability. However, when the compound of the present invention is used, as the amount of replenishment is reduced, the adhesion property tends to be slightly improved.

Example 6 The total silver amount of the color photographic light-sensitive material in Example 4 was changed as shown in Table 6, and treatment No. 4-1 (No. 6-1 to
6-5), No, 4-6 (No, 6-6 to 6-11
) and No. 4-10 (No. 6-12 to 6-15)
) was evaluated in the same manner as in Example 4.

However, the total amount of silver was varied by the ratio between each layer so that the amount of silver was as shown in Table 6.

The results are shown in Table 6.

Table Green Transmission Density After Storage - Green Transmission Density Before Storage As is clear from Table 6, when the amount of silver is 5.0 g/rrI' or more, the adhesion tends to decrease, and this tendency is particularly 6-1 to 6-1 using thiosulfate as an agent
5. It is noticeable in O. In the case of 0g/g or less, it can be seen that the effect is more pronounced when the compound of the present invention is used as a stabilizing solution and thiocyanate is used as a fixing agent.

Example 7 Cyan coupler C-2 in the photosensitive material used in Example 4 was replaced with the following BAR-1 to BAR-3 and the following BA-Ag-1, B
Evaluations similar to those in Example 3 were carried out by replacing A-Ag-2 with equimolar amounts of each.

As a result, the effect was the same as in Example 3, but the effect on fixation was more pronounced when treated with the stabilizer containing the compound of the present invention than with the stabilizer containing formalin. .

AR-1 ('+11 SCHI C1l, COO11 AR-2 n+1 AR-3 BA-Ag-1 +1ooc CHzCI(-SAg BA-Ag-2 C, Il, C00I+ [Effects of the Invention] According to the present invention, rapid processing It is possible to provide a method for processing a silver halide color photographic light-sensitive material, which is possible, has excellent liquid storage stability and processing stability, and can further achieve low pollution.

Claims (5)

[Claims] (1) After imagewise exposure of the silver halide color photographic light-sensitive material,
In a method for processing a silver halide color photographic light-sensitive material which is subjected to a color development process, then processed with a bleach-fix solution, and then processed with a stabilizing solution, the stabilizing solution does not substantially contain formalin, and the stabilizing solution does not contain hexafluoride. Contains at least one compound selected from methylenetetramine compounds and compounds represented by the following general formulas [F-1] to [F-10], and the pH of the stable solution is 7.5 or higher. Characteristic processing method for silver halide color photographic materials. General formula [F-1] ▲There are numerical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 to R_6 each represent a hydrogen atom or a monovalent organic group. ] General formula [F-2] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula [F-3] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula [F-4] ▲ Contains mathematical formulas, chemical formulas, tables, etc. Yes▼ [In the formula, R_7 represents a hydrogen atom or a methylol group. ] General formula [F-5] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [F-6] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, V_1 and W_1 represent electron-withdrawing groups. , or V_1 and W_1 may be combined to form a 5- or 6-membered nitrogen-containing heterocycle. Y_1 represents a hydrogen atom or a group that is eliminated by hydrolysis. Z is a nitrogen atom and ■C=O
Represents a group of nonmetallic atoms necessary to form a monocyclic or fused nitrogen-containing heterocycle with the group. ] General formula [F-7] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_8 represents a hydrogen atom or an aliphatic group, and R_9
and R_1_0 each represent an aliphatic group or an aryl group,
R_9 and R_1_0 may be combined with each other to form a ring. Z_1 and Z_2 are each an oxygen atom, a sulfur atom or -
Represents N(R_1_1)-. However, Z_1 and Z_2 are never oxygen atoms or -N(R_1_1)- at the same time. R_1_1 represents a hydrogen atom, a hydroxy group, an aliphatic group, or an aryl group. [ In the formula, R_1_2 represents a hydrogen atom or an aliphatic hydrocarbon group, V_2 represents a group that is eliminated by hydrolysis, and M
represents a cation, W_2 and Y_2 each represent a hydrogen atom or a group that is eliminated by hydrolysis, n represents an integer of 1 to 10, and Z_3 is a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a group that is eliminated by hydrolysis. Represents a group that leaves, R_
1_3 represents an aliphatic hydrocarbon group or an aryl group. Z_
3 may be combined with R_1_3 to form a ring. ] (2) The method for processing a silver halide color photographic material according to claim 1, wherein the hexamethylenetetramine compound is a compound represented by the following general formula [A-1] or a salt thereof. General formula [A-1] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, A_1 to A_4 represent a hydrogen atom, an alkyl group, an alkenyl group, or a pyridyl group, and l represents 0 or 1. ] (3) The amount of coated silver in the silver halide color photographic light-sensitive material is 5.5% per 1 m^2 of the silver halide color photographic light-sensitive material.
3. The method for processing a silver halide color photographic material according to claim 1, wherein the silver halide color photographic material has a content of 0 g or less. (4) The method for processing a silver halide color photographic material according to claim 1, 2 or 3, wherein the bleach-fix solution contains at least 0.1 mol/l of thiocyanate as a fixing agent. Processing method for silver chemical color photographic materials. (5) The silver halide color photographic light-sensitive material according to claim 1, 2, 3 or 4, wherein the amount of replenishment of the bleach-fixing solution is 800 m or less per 1 m^2 of the silver halide color photographic light-sensitive material. processing method.