JPH04194856A - Processing method for silver halid color photosensitive material - Google Patents

Abstract

PURPOSE:To perform processing by means of common stabilizing liquid by processing at least two different kinds of photosensitive materials each having a specific total coated silver amount by means of stabilizing liquid containing a specific compound and at least one kind of a compound selected from the specific compound group. CONSTITUTION:A material A having a total coated silver amount of 2 - 10g/m<2> contained in a silver halid color photosensitive material and at least two differ ent materials selected from materials B having a total coated silver amount of 1g/m<2> or less are treated by means of stabilizing liquid containing a hexamethylenetetramine compound and at least one kind of a compound selected from a compound group expressed by formulas I and II. In the formula I, R1 - R6 represent a hydrogen atom or a univalent organic group. In the formula II, each of R71 - R75 represents a hydrogen atom or a methylol group. Further, X represents an oxygen atom or an sulfur atom. A compound expressed by a formula III or salt thereof is listed as a hexamethylenetetramine compound.

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 materials, and more specifically, the generation of sludge and scum in a stabilizing solution is suppressed, and the storage of color negative film is improved. The present invention relates to a method for processing a silver halide color photographic material, which prevents the occurrence of yellow stain and fading of magenta dye, and suppresses dark fading of cyan dye due to storage of color paper.

[Conventional technology]

The silver halide color photographic light-sensitive material is color photographic Xff1.
Developing is carried out at small shops called image studios and minilabs. Generally, a color negative film for photography is developed to create a negative image, this negative image is printed on a color negative photosensitive material for printing using a printing machine, and the photosensitive material is developed in a developing device different from the above-mentioned developing device. , a positive image is obtained on the photosensitive material. The process of obtaining color photographic images in this way requires the installation of equipment for three processes: an automatic developing machine for color negative film, an automatic developing machine for color negative paper, and an automatic photographic printer. Particularly, among these devices, around automatic processors, there is a designated space for work space around the equipment. The installation area required for replenishment work, such as the space required to dissolve and adjust the replenisher, the space to transfer the dissolved replenisher to the replenishment tank, and the space required to adjust the replenishment cock, takes up a considerable amount of space within the photofinishing laboratory. occupies .

Furthermore, the developing process for photosensitive materials consists of two or more processing steps as described above, and a replenisher is prepared for each of them, which requires a large amount of space as described above. These replenishment operations require a large amount of time and require frequent dissolution and adjustment of the replenisher.

In addition, when an automatic developing machine for color negative film and an automatic developing machine for color negative paper are used separately, each automatic developing machine has ancillary equipment such as a temperature control device, a processing liquid circulation device, a filter device, a replenishment tank, Replenishment devices and the like are required for each, which goes against the trend of making automatic processors more compact and reducing costs. As one means for solving such problems, automatic processors are known that can process negative and positive light-sensitive materials using the same processing bath or the same replenisher. Various problems arise in automatic developing machines.

Particularly when the stabilizer is treated with a common tank or a common replenisher, the generation of sludge and scum in the stabilizer can significantly clog the filters of automatic processors and the like, causing malfunctions. Furthermore, in color paper, it has been found that magentastin occurs after processing and that the stability of dye images, particularly the fading of cyan dyes, is significant.

According to the studies conducted by the present inventors, the former problem is caused by a decrease in the stability of the stabilizer itself when processing light-sensitive materials with different amounts of silver or silver halide compositions, and the latter problem is caused by the fact that the stabilizer Years of research have revealed that this is caused by formaldehyde in the water. However, formaldehyde is effective in stabilizing dye images, especially in preventing yellow stain, and has traditionally been used in processing color negative films, making it extremely difficult to remove it from the stabilizing bath. It was a difficult problem.

[Purpose of the invention]

Accordingly, the first object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which enables at least two types of light-sensitive materials having different amounts of coated silver to be processed with a common stabilizing solution. A second object is to provide a method for processing silver halide color photographic materials in which the generation of sludge and scum in a stabilizing tank is improved. Furthermore, the third object is to provide a method for processing silver halide color photographic materials in which the occurrence of yellow stain due to storage of color negative films after processing is suppressed and fading of magenta dye is also prevented. teeth.

An object of the present invention is to provide a method for processing a silver halide color photographic material, which can suppress dark fading of a cyan dye during storage of color negative paper after color processing.

Other objectives will become apparent in the description below.

[Means to solve the problem]

The method for processing a silver halide color photographic light-sensitive material of the present invention which achieves the above object is characterized in that the total coating amount of halogenated silver contained in the silver halide color photographic light-sensitive material is 2 g/d to 10 g/m2. Silver color photographic material (
A) and a silver halide color photographic material (B) in which the total coating amount of silver halide contained in the silver halide color photographic material is 1 g/rn' or less. , a hexamethylenetetramine compound, and a stabilizing solution containing at least one compound selected from the group of compounds represented by the following general formulas [F-1] to [F-10].

[In the formula, R1-R6 each represents a hydrogen atom or a monovalent organic group] General formula [F-3] R+.

General formula [F-4] [In the formula, R71 to R+s each represent a hydrogen atom or a methylol group, and further, X represents an oxygen atom or a sulfur atom.] General formula [F-5] [In the formula, (1) and Wl each represents a hydrogen atom, a lower alkyl group, or an electron-withdrawing group;

vl and Wj may be combined to form a 5-membered or 6i nitrogen-containing heterocycle, and Yl represents a hydrogen atom or a group that is eliminated by hydrolysis.

Z represents a nonmetallic atom group necessary to form a monocyclic or condensed nitrogen-containing heterocycle with a nitrogen atom and a C═O group, [F-7] [wherein R8 is a hydrogen atom or R9 and RIG represent an aliphatic group, each aliphatic group represents an aryl group, R9 and R
IO may be bonded to each other to form a ring, ZJ and Z
2 each represents an oxygen atom, a sulfur atom, or -N(Rh)-, however, Zl and 22 are never oxygen atoms at the same time, R11 represents a hydrogen atom, a hydroxy group, an aliphatic group, or an aryl group.] General formula F-8] General formula [F-9] 17-0 (-CH20Y2 General formula [F-10] [In the formula, R12 represents a hydrogen atom or an aliphatic hydrocarbon group, and v2 is hydrolyzed M represents a cation, and W2 and Y? each represent a hydrogen atom or a group that leaves by hydrolysis.

n represents an integer of 1 to 10, 23 and R13 each represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a group that is eliminated by hydrolysis; aZ3 may be combined with RI3 to form a ring; ] A preferred embodiment of the present invention is characterized in that at least 50 mol% of the silver halide grains contained in the silver halide emulsion layer of the silver halide color photographic light-sensitive material (B) are silver chloride. .

[For production]

Color negative film and color negative paper are currently processed in separate processors. However, from the viewpoint of space saving, it is preferable to process in the same processing bath, and the liquid management can be halved.However, if color negative film and color negative paper are processed in the same bath, various problems will occur.

In particular, if a stabilizer bath is shared, high-Ag photosensitive materials and low-Ag photosensitive materials are processed unevenly, resulting in unstable processing and sludge caused by silver is likely to occur in the stabilizer bath. Moreover, magenta tint tends to occur after processing. This is particularly likely to occur if formaldehyde is present.

On the other hand, when processing color negative films, if formaldehyde is not used, it will cause yellow stain and fading of magenta dyes due to storage, but in the case of color negative paper, the presence of formaldehyde may actually worsen the dark fading of cyan dyes. It turns out.

By adding the compound of the present invention to the stabilizer bath,
The generation of sludge and scum is also improved, and yellow stain and fading of magenta dye due to storage of color negative film and dark fading of cyan dye of color negative paper are also eliminated.

The hexamethylenetetramine compound used in the stabilizing liquid in the present invention is preferably a compound represented by the following general formula [A-1] or a salt thereof.

In the general formula [A-1], each group represented by A1 to A4 includes a substituent. Examples of the substituent include a carbamoyl group, a halogen atom such as a carbon atom, and an aryl group such as a phenyl group. , hydroxyl group, carboxyl group, oxycarbonyl group such as methoxycarbonyl group, and the like.

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

Salts of the compound represented by the general formula [A-1] include inorganic m salts such as hydrochlorides, sulfates, and nitrates, organic acid salts such as phenol salts, double salts or complex salts with metal salts, hydrated salts, molecular Examples include inner salt.

Specifically, the compound represented by the general formula [A-1] is a compound represented by Beilsteins Handbuch der Organadiene Hemi.
Compounds described in Vol. 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 its salt are listed below.

A-1-I A-1-2A-1-3A
-1-4 A-15A-1-6 C)-].

Although the compound of general formula [A-1] is easily available as a commercial product, it can also be easily synthesized using the method described in the above-mentioned literature.

The compound of general formula [A-1] may be used alone or in combination of two or more, and the amount added is 0.01 per 1 g of treatment liquid.
The range of g to 20 g is preferred.

Next, general formula [F-1]-general formula [F
-10] will be explained.

In the general formula [F-1], R, -R, and 6 each represent a hydrogen atom or a monovalent organic group, and examples of the monovalent organic group include an alkyl group, an aryl group, an alkenyl group, and an alkynyl group. , aralkyl group, amino group, alkoxy group,
Hydroxy group, acyl group, sulfonyl group, alkylthio group, arylthio group, heterocyclic residue, carbamoyl group,
Examples include a sulfamoyl group and an alkylamino group.

These -valent organic groups have substituents (e.g., hydroxy group, acyl group, sulfonyl group, halogen atom, amino group,
It may have a carboxy group, preferably a hydroxy group or a halogen atom. or,
The total number of carbon atoms of the substituents represented by F−+ to R6 and 17 are I
I prefer O to J or I/I.

The group R,, R3, R, and the group R2, R4, 'R, may be the same or different, and it is preferable that one or all of the groups are hydrogen atoms.

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

Margin below F-1-I CH, C) 1.
OH ■ F-1-2CH.

F-1-4CH, -C)l-C)l.

F-1-508 ■ F-1-6C, MS ■ C1116-NN　C,z)Is F-1-7So,)1 F-1-8C0CH.

■ F-1-9oH C)1. CHCH.

F-1-12C)l, C)1. CH, NH.

HJCHtCHtL)1. N+VA C14+C
LCHJ)I.

F-1-13Co-C)I=CI(.

F-1-140CH.

F-1-16CM□OH F-1-17H CH,OH F-1-20C) l', CN ] The triazine compound represented by these is preferably used in an amount of 0.05 g to 50 g, more preferably 1 g to 20 g, per stabilizer IQ.

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

(F-2-1) Dimethylol urea (F-2-2) ) Dimethylol urea (F-2-3)
Monomethylol urea (F-2-4) Tetramethylol urea (F-2-5) Dimethylol thiourea (
F-2-8) Monomethylolthiourea CF-3-1
)) Limethylolmelamine (F-3-2) Tetramethylolmelamine (F-3-3) Pentamethylolmelamine (F-3-4) Hexamethylolmelamine (F-3-5) Monomethylolmelamine (F-
4-1) Dimethylolguanine (F-4-2)
Monomethylol guanidine (F-4-3)) Limethylol guanidine (F-4-3) Addition amount is 0.05 to 2 per liter of stabilizer.
It is preferably 0 g, more preferably 0.1 to 10 g/cross, and within this range the effects of the present invention can be effectively achieved.

In the general formulas [F-5 and [F-6], the electron-withdrawing groups represented by vl and Wl include Hammett (
7) CRP value (Lange'a Handbook o
fChemistr712th ed, Vol. 3. C
,) lansch & A, Leo, 5ubstitu
ent Con5tants for Correla
tion Analysis Chemistry
and Biology (Jone Wiley &
5oz.

New York 1979)) is positive, and specifically, acyl groups (e.g., acetyl, benzoyl, monochloroacetyl, etc.), alkoxycarbonyl groups (e.g., ethoxycarbonyl, methoxyethoxycarbonyl, etc.), Aryloxycarbonyl group (
(e.g., phenoxycarbonyl, p-chlorophenoxycarbonyl, etc.), carbamoyl group (e.g., tomethylcarbamoyl, N,N-tetramethylenecar/hemoyl,
h-phenylcaroctamoyl, etc.), cyan group, alkylsulfonyl group (e.g., methanesulfonyl, ethanesulfonyl, etc.), arylsulfonyl group (e.g., benzenesulfonyl, P-)luenesulfonyl, etc.), sulfamoyl X (e.g., sulfamoyl, N-methylsulfamoyl, N,N-pentamethylenesulfamoyl, etc.). Examples of lower alkyl groups include methyl, ethyl, propyl, butyl, and the like.

The group shown by Yl that leaves by hydrolysis is:
For example, trialkyl-substituted silyl groups (e.g., trimethylsilyl L4), acyl groups (e.g., acetyl, benzoyl, monochloroacetyl, trifluoroacetyl, etc.), sulfate groups, aminocarbonyl groups (e.g., N, N
), N-methylcarbonyl, N-methylcarbonyl, N-phenylcarbonyl, etc.), sulfonate 2! (For example, methanesulfonate, benzenesulfonate, P-toluenesulfonate, etc.).

The 5- or 6-membered nitrogen-containing heterocycle formed with the nitrogen atom represented by 2 and the >C=0 group is [Cl84]
, [02N3], [C3N21, [CaN]
, [C2Nn1.

[03N31. [C4N? ], [CsN], [
C2N20], [03NO].

[03N20], IC4NO], [C2)
12s], [C3NS], [C3N2S]
.

[C3N2S], [G3N5al, [CaNSe]
, [C:3NTe1 and other monocyclic rings,
IC:3N2-C61, [04N-06].

[CJ-03N2], [03N 2-C:3N21
, [C3NS-C6], [05N-C5N]
.

Examples include integrated rings consisting of elemental compositions such as [C3N-C61, fcaN2-C6], and on these rings, for example, alkyl groups (e.g., methyl, ethyl, methoxyethyl,
benzyl, carboxymethyl, sulfopropyl, etc.), aryl groups (e.g., phenyl, p-methoxyphenyl, etc.), hydroxy groups, alkoxy groups (e.g., methoxy,
ethoxy, methoxyethoxy, etc.), aryloxy2!
(e.g., phenoxy, P-carboxyphenyl, etc.),
Carboxine group, sulfo group, alkoxyl carbonyl 2!
(for example.

Methoxycarbonyl, ethoxycarbonyl? ).

Aryloxycarbonyl group (e.g., phenoxycarbonyl, etc.), amino group (e.g., N,N-dimethylamino, N-ethylamino, N-phenylamino, etc.), acylamide group (e.g., acetamide, benzamide, etc.)
, carbamoyl group (e.g. carbamoyl, N-methylcarbamoyl, N,N-tetramethylenecarbamoyl, etc.), sulfonamide group (e.g. methanesulfonamide, benzenesulfonamide F, etc.), sulfamoyl group (e.g. N-ethylsulfonamide), moyl, N,N-dimethylsulfamoyl, etc.), alkylsulfonyl groups (e.g., methanesulfonyl, ethanesulfonyl, etc.), arylsulfonyl groups (e.g., benzenesulfonyl, p-toluenesulfonyl, etc.), acyl groups (e.g., acetyl, pentyl, etc.).

In general formula [F-5], the 5M or 6-membered nitrogen-containing heterocycle that can be formed via vl and Wl, which are divalent electron-withdrawing groups, respectively, has the following general formula [F-5- a
] are listed.

General formula [F-5-a] In the general formula [F-5-a], vl and Wl are each -
CO-, -Co-0-, -3o-, -5O2 or -C,
It represents an S-group, and Zl represents a group of nonmetallic atoms necessary for bonding with V and W to form a 5- or 6-membered monocyclic or condensed ring.

The 5- or 6-membered monocyclic or condensed ring formed by zl can have any substituent, such as an alkyl group (for example, methyl, ethyl,
methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.), aryl groups (e.g., phenyl, p-methoxyphenyl, etc.), hydroxy groups, alkoxy groups (e.g., methoxy, ethoxy, methoxyethoxy, etc.), aryloxy groups (e.g., phenoxy, p-carboxyphenyl, etc.), carboxy group, sulfo group, alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (e.g.,
Phenoxycarbonyl! 4), amine groups (e.g. N,
N-dimethylamino.

N-ethylamino, N-phenylamino), acylamido groups (e.g., acetamide, benzamide, etc.), carbamoyl groups (e.g., carbamoyl).

N-methylcarbamoyl, N,N-tetramethylenecarbamoyl, etc.), sulfonamide groups (e.g., methanesulfonamide, benzenesulfonamide F, etc.), sulfamoyl groups (e.g., N-ethylsulfamoyl, N,N
-dimethylsulfamoyl, etc.), alkylsulfonyl groups (e.g., methanesulfonyl, ethanesulfonyl, etc.),
Arylsulfonyl groups (e.g. benzenesulfonyl,
(P-) luenesulfonyl, etc.), and acyl groups (eg, acetyl, pentyl, etc.) # groups.

Specific examples of the compounds represented by the general formulas [F-5] and [F-6] used in the present invention are shown below, but the invention is not limited thereto.

F-5-7F-5-8 F-5-9F-5-1゜1100cmC)1. NH-C)1. OH, (CM))
, N-C) 1108F-5-11F-5-12 C11,-NH-C)1. OHC, l+, 0CONH-
CII, 0H12-5-HF-5-14 C)1. OH H1OH Addition of the compound represented by the general formula [F-5] or [F-6] is preferably 0.01 to 20 g, more preferably 0.03 to 15 g, particularly preferably 0.05 g per stabilizer.
~log.

In the general formula [F-7], R8, R9 and RH
Examples of the aliphatic group represented by include saturated alkyl groups (for example, unsubstituted alkyl groups such as methyl, ethyl, butyl, and benzyl, carboxymethyl, hydroxymethyl,
(substituted alkyl groups such as methoxyethyl), unsaturated alkyl groups (eg, allyl, 2-butenyl, etc.), cyclic alkyl groups (eg, cyclopentyl, cyclohexyl, etc.), and the like.

The aryl groups represented by R9, RIG and R1+ include substituted and unsubstituted ones, and examples of substituents include alkyl groups (e.g., methyl, ethyl, methquinethyl, benzyl, carboxymethyl, sulfopropyl, etc.), aryl groups, etc. (e.g. phenyl, p-methoxyphenyl calyx)
, hydroxy group, alkoxy group (e.g. methoxy, ethoxy, methoxy ethoxy9), aryloxy group (e.g. phenoxy, P-carpogysiphenyl, etc.), carboxy group, sulfo group, alkoxycarbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl, etc.), amino groups (e.g., phenoxycarbonyl, etc.).

N,N-dimethylamino, N-ethylamino, N-phenylamino, etc.), acylamido groups (e.g., acetamide, benzamide, etc.), carbamoyl groups (e.g., caroctamoyl, N-methylcaroctamoyl, N,N-tetra methylene carpamo, fluorophore), sulfonamide F group (e.g. 1. methanesulfonamide, benzenesulfonamide, etc.), sulfamoyl group (e.g. toethylsulfamoyl, N,N-dimethylsulfamoyl, etc.), alkylsulfonyl Any group selected from groups such as (for example, methanesulfonyl, ethanesulfonyl, etc.), arylsulfonyl Can be mentioned.

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 heteroatoms.

As RB, a hydrogen atom is preferable.

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.

Below margin 1'-7-I CH, OH Door 2 P -7-3 Door 4 ■? -7-5 C=Ha 1'-7-7 曵CH,OH F-7-11 F-7-12 The general formula [F-71] is shown in the margin below.
Preferably 0.01 to 20g per sentence, more preferably 0
．． 03 to 15 g, particularly preferably 005 to 10 g.

In the general formulas [F-81 to [F-101], RH,
As the aliphatic hydrocarbon group represented by R13 and z3,
Saturated alkyl groups (e.g., unsubstituted alkyl groups such as methyl, ethyl, butyl, and substituted alkyl groups such as carboxymethyl, methoxymethyl, methoxyethyl, hydroxyethyl, benzyl, etc.), unperturbed alkyl groups (e.g., allyl, 2-butenyl, etc.), cyclic alkyl groups (e.g.,
cyclopentyl, cyclohexyl, etc.).

The aryl group represented by R13 and z3 may be substituted, and examples of the substituent include an alkyl group (methyl, ethyl, methoxyethyl, hensyl, carboxymethyl, sulfopropyl, etc.), an aryl group (for example, phenyl, p-
methoxyphenyl, etc.), hydroxy groups, alkoxy groups (
For example, methoxy, ethoxy, methoxyoxy, etc.)
, aryloxy group (e.g., fenoquine, p-carboxyphenyl, etc.), carboxy group, sulfo group, alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl, etc.), Amine groups (e.g. N
, tosimethylamino, N-ethylamino, N-phenylamino, etc.), anuramide (e.g., acetamide,
hesozamide, etc.), carbamoyl groups (e.g., Cal, <
Moyle.

N-methylcarbamoyl, N,N-tetramethylenecarbamoyl, etc.), sulfonamide)1. ! , (e.g., methanesulfonamide, hensensulfonamide, etc.), sulfamoyl group (e.g., toethylsulfγmoyl, N,
N-diethylsulfamoyl, etc.), alkylsulfonyl groups (for example, methanesulfonyl, ethanesulfokol, etc.)
, arylsulfonyl M (eg, hensensulfonyl, p-toluenesulfonyl, etc.), acyl (eg, acetyl, henzyl, etc.), and the like.

V2. Examples of groups that are eliminated by hydrolysis represented by R2, Yl and z3 include 7-syl groups (e.g., 7-cetyl, 7-cetyl, )-lifluoroacetyl, monochloroacetyl-%'),) real Kylsilyl X (eg, trimethylsilyl, etc.) may be mentioned.

The ring formed by R and 3 bonding with 21 is a 5- to B-membered saturated ring or Kurabatake ring, and includes those in which a part of the bonded carbon chain is @ replaced with other heteroatoms. .

Specific examples include rings such as l,2-dioxacyclobencune, dioxane, trioxane, tetraoxane, and benzdioquinrane.

Cations represented by M-C include 1, for example, hydrogen ions,
Alkali metal ions (e.g. lithium, sodium,
ion of potassium moiety), alkaline earth metal ion (e.g., ion of magnesium, calcium, etc.), ammonium ion, organic ammonium ion (e.g., 1-ethylammonium), ribrobylammonium, tetramethylammonium ammonium ions), pyrinnium ions, etc.

General formula [F-8] - [F-1011m, R1?
The aliphatic hydrocarbon group represented by is preferably a lower alkyl group having 1 or 2 carbon atoms, and more preferably R12 is an * elementary atom.

Specific examples of compounds represented by the general formulas [F-8co to [F-103] are shown below, but the compounds are not limited to these compounds.
゛・ Below margin P-9-1 to 9-2 CI13COO(CH,CI)acOcH,C)l,C
C00(C,O),C0C)I.

f-! L:l
r-9-4CH,Coo(CH,O),C0CH,,
No(CH,O),. HF-9~5
19-6C12C)1. Coo(CH
, 0), C0CH, Cl2I to-I
F・1O-2P-1o-7F
io8 F -10-10 F -10-11 F -10-12 F -10-13 F -10-14 F -10-15 F -10-16 F -10-17 F -10-18 F -10- 19 F -10-20 F -10-21 F -10-22 F-10-23 The amount of the compound represented by the general formula [F-8], [F-9] or [F-10] depends on the treatment liquid. 0.01-20g per party
is preferable, more preferably 0.03 to 15 g, particularly preferably 0.05 to log.

In the present invention, it is preferable that the stabilizing solution contains a chelating agent having a chelate stability constant of 8 or more for iron ions.
llen * A.E. Martell, “5ta
bilit7 Con5tants of Metal
-ion Complexes'', TheChemi
cal 5ocity, London (1984)
. S, C: haberek @A, E, Martell
Author, “Organic Sequestering
"AgentS", a constant generally known by Wiley (1959) and others.

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 (Fe'').

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. Namely, ethylenediaminediorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminenibropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diamino Prohanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic 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-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium birophosphate, Examples include sodium tetrapolyphosphate, sodium hexametaphosphate, and particularly preferred are diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid and the like, among which 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

The amount of the above chelating agent used is 0, O1 to 5 per liter of stabilizer.
0. is preferable, and more preferably good results can be obtained in the range of 0.05 to 20 g.

Further, preferred compounds to 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 phosphate, ammonium phosphate, ammonium phosphite, and fluoride. Ammonium, ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, Ammonium lauric tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarhemate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfate, 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-) linitrophenol ammonium, etc. These can be used alone or in combination of two or more, and the amount of ammonium compound added is 1 for the stabilizer! ; The range is preferably 0.001 mol to 1.0 mol per L, more preferably 0.001 mol to 1.0 mol.
The range is from 0.002 to 2.0 moles.

Further, it is preferable that the stabilizing liquid contains a sulfite. The sulfite may be any organic or inorganic substance as long as it releases sulfite ions, but an inorganic salt is preferable. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and /\hydrosulfite. It will be done. It is preferable that the above sulfite is added to the stabilizing solution in an amount of at least IXIG-3 mol/R, more preferably 5X 1G-3 mol/R.
-10-1 mol/l is added, 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 preferably contains a metal salt in combination with the chelating agent.

Ba, Ga, Ce, Co, In, La, Mn
, Ni, Bi, Pb, Sn.

There are metal salts of Zn, Ti, Zr, Mg, An or Sr, which can be supplied as inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates, or water-soluble chelating agents. The amount used is per stabilizer In.
The range is preferably from 10-4 to IX 10-1 mol, more preferably from 4X 10-' to 2X 10-2 mol.

Organic #salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphates, borates, hydrochloric acid, sulfates, etc.), etc. can be added to the stabilizing solution. .

These compounds may be added in any combination of amounts that are necessary to maintain the pH of the stabilizing bath and do not adversely affect the stability of color photographic images during storage and the generation of precipitates. do not have.

In the present invention, known antifungal agents such as 5-chloro-2-methylinthiazoline 3-one, benzinthiazoline 3-one, and benzinthiazoline 1 can be used in combination within the range that does not impair the effects of the present invention.

The stabilizing liquid may contain a surfactant. Examples of the surfactant include compounds represented by formulas [I] to [II] described in JP-A-62-250449 and water-soluble organic siloxane compounds.

In the process of the present invention, silver may be recovered from the stabilizing solution.

In addition, the stabilizing solution can be subjected to ion exchange treatment, electrodialysis treatment (see Japanese Patent Application No. 59 J6352) and reverse osmosis treatment (Japanese Patent Application No.
No. 241053, No. 62-254151, JP-A-2-
132440) etc. is also a preferred embodiment of the present invention. It is also preferable to use water that has been previously deionized for use in the stabilizing solution, as this improves the mildew-proofing properties of the stabilizing solution, the stability of the stabilizing solution, and the image storage stability. Any means of deionization treatment may be used as long as it reduces the Ca and Mg ions in the washed water after treatment to 5 ppm or less, but for example, treatment with an ion exchange resin or reverse osmosis membrane may be used alone or in combination. preferable. Ion exchange resins and reverse osmosis membranes are described in detail in Kokai Technical Report No. 87-1984.

The salt concentration in the stabilizing solution is preferably 11,000 pp or less, more preferably 800 pp or less in order to achieve the effects of the present invention.

It is preferable that a soluble iron salt be present in the stabilizing liquid in order to achieve the effects of the present invention. Soluble iron salts are present in the stabilizing solution at least 5
It is preferably used at a concentration of
3 mol/day, more preferably 12X'l
It ranges from O''3 to 100X 10-3 mol/state.

In the present invention, the pH of the stabilizing solution is 5.5 to 12.0.
The pH is preferably in the range of 7.0 to 10.0 in order to achieve the effects of the present invention. The pH adjusting agent that can be contained in the stabilizing liquid may be any commonly known alkaline agent or acidic agent.

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. In addition, it is preferable that the processing time is 150 seconds or less,
More preferably it is 3 seconds to 120 seconds, most preferably 6 seconds to 90 seconds.

The replenishment amount of the stabilizing solution is preferably 1000 m3 or less per rn' of the light-sensitive material, more preferably 150 mM or more and 500+af1 or less, from the viewpoint of rapid processing properties and dye image storage stability.

The stabilization tank is preferably composed of a plurality of tanks, preferably from 2 tanks to 6 tanks, particularly preferably 2 to 3 tanks, and even more preferably 2 tanks. It is preferable to use a method in which the water is supplied and flowed from the pre-bath to the water.

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.

In the present invention, the object of the present invention can be more effectively achieved when a chloride is contained in an amount of at least 3 x 10-2 mol per lfL of color developing solution, especially when processing a light-sensitive material with a high silver chloride concentration. Especially 3.5 per sentence of color developer
X 10-2 to 20X 10-2 mol, especially per liter of color developer 4. OX 10-2~12X 1
Good results can be obtained with 0-2 mol.

The above-mentioned enhancer may be any compound as long as it releases chloride ions in a color developing solution, and specific compounds include potassium chloride, sodium chloride, lithium chloride, bugnesium chloride, and the like.

Usually, sulfite is used as a preservative in color developer, but when the sulfite concentration is less than 10-2 mol per color developer, silver chloride is the main component. It is possible to suppress the decrease in color density that is thought to be caused by the dissolution physical development of photosensitive materials, and the decrease in storage ability is also very slight, making rapid processing possible using photosensitive materials that mainly contain silver chloride. Since it is possible to provide a color developer or a method for processing silver halide color photographs using the color developer, a sulfite concentration of 18×10 −2 mol/liter or less in the color developer is preferably used in the present invention. Furthermore, this effect is better exhibited when the amount is 1Xl0-2 mol/or less, more preferably 4
X 10-3 mol/liter or less.

Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

However, when the silver halide color photographic light-sensitive materials have different silver halide compositions, for example, when the light-sensitive material (A) is a silver iodobromide emulsion and the light-sensitive material (B) is silver chlorobromide or silver chloride, It is preferable that the color developing solutions for the photosensitive material (A) are treated in separate baths, and in this case, the sulfite concentration in the color developing solution for the light-sensitive material (A) is 5×10 −3 mol/liter or more, preferably 1×10
−2 mol/liter or more, particularly preferably 2×101 mol/liter or more.

As the color developing agent used in the color developer of the present invention, a P-2 engineered nylene diamine compound having a water-soluble group is preferably used because it exhibits the desired effect of the present invention well and causes less fogging. It will be done.

A p-phelenediamine compound having a water-soluble group is
Compared to paraphenylenediamine compounds that do not have water-soluble groups such as N,N-diethyl-p-phenylenediamine, they not only do not contaminate photosensitive materials and are less likely to irritate the skin, but also In particular, by combining it with the color developing solution of the present invention, the objects of the present invention can be achieved more efficiently.

Examples of the water-soluble group include those having at least one on the noamino group of a p-phenylenediamine compound or on the benzene nucleus, and a specific example of the water-soluble group is -(C:H2). '-CH20H1-(CH2)'-NH3O2-(OH2). ′-(H
3, -(C:H2)n'-0-(CH2)n'-C:H
3, -(CH2CH20)n'Gs'82s'41(1
1' and n' each represent an integer greater than or equal to 0, )
Preferred examples include -COOH group and -503H group.

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

[Example color developing agent] K] 11 N11° NH2 N11° N.H.

H11! Nil.

NH8 NHL +18° Nil.

N.H.

Among the color developing agents exemplified above, exemplification No. (C-
1) , (C-2), (C-3), (C-4), (C-
6), (C-7) and (C-15), particularly preferably No, (C-1), (C-,3)
It is.

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

The color developing agent having a water-soluble group that is preferably used in the present invention is usually 0.5X 10 per color developer.
It is preferable to use -3 mol or more, especially in the range of 10-2 to 2 x 10-1 mol, but from the viewpoint of rapid processing, the amount is 1.5 x 10-2 to 2 x 1 per batch of color developer.
A range of 0-1 mol is more preferred.

The color developing agent may be used alone or in combination of two or more, and if desired, a black and white developing agent such as phenidone,
4-hydroxymethyl-4-methyl-1-phenyl-3
- May be used in combination with pyrazolidone, metol, etc.

Furthermore, instead of using the above-mentioned color developing agent in the color developing solution, a color developing agent can be added to the photographic material, and in that case, the color developing agent used may include a dye precursor. Japanese Patent Application Publication No. 5
Those described in No. 8-85429, No. 58-24137, etc. are used, and specifically, for example, 2', 4'-bismethanesulfonamide-4-diethylaminodiphenylamine, 2'-methanesulfonamide-4' -(2,4
, fl-triinpropyl)benzenesulfonamide-
2-Methyl-4-N-(2-methanesulfonamidoethyl)ethylaminodiphenylamine, 2'-methanesulfonamide-4'=(2,4,8-triisopropyl)
Benzenesulfonamido-4-(hydroxytrisethoxy)diphenylamine, 4-N-(2-methanesulfonamidoethyl)ethylamino-2-methyl-2',4
'-Bis(2,4,64-liinpropyl)benzenesulfonamide diphenylamine, 2,4'-bismethanesulfonamide-4-N,N-diethylaminodiphenylamine, 4-n-hexyloxy-2'-methanesulfonamide- 4'-(2,4,8-triinpropyl)benzenesulfonamide diphenylamine, 4-methoxy-2'-methanesulfonamide F-4'-(2,4,8-
) lyisobrovir) benzenesulfonamide diphenylamine, 4-diethylamine-4'-(2,4,8-)
lyisopropylbenzenesulfonamide) diphenylamine, 4-n-hexyloxy-3'-methyl-4'-
(2,4,6-)lyisopropylbenzenesulfonamido)diphenylamine, 4-N,N-diethylamine-
4'-(2,4,6-Doliisobrobylbenzenesulfonamido)diphenylamine.

Examples include 4-N,N-dimethylamino-2-phenylsulfonyl-4'-(2,4,8-)lyisopropylbenzenesulfonamido)diphenylamine.

The amount of the dye precursor added to the photosensitive material is preferably 0.5 to 22 g, more preferably 4 to 12 mg per 100 crn' of the photosensitive material.

In the present invention, the processing time of the color development step may be any time, but in the case of a light-sensitive material having a total coated silver amount of 2 g/m2 or more, a time of 10 seconds to 4 minutes is usually used, and preferably 10 seconds to 4 minutes. In the range of 20 seconds to 200 seconds, more preferably in the range of 30 seconds to 200 seconds, most preferably in the range of 45 seconds to 2
The range is 00 seconds. Furthermore, the total coating silver amount of the present invention is 1
For photosensitive materials of g/m2 or less, the time is usually 3 seconds to 4 minutes, preferably 5 seconds to 2 minutes, more preferably 7 seconds to 60 seconds, and most preferably 8 seconds to 2 minutes.
The range is 50 seconds.

The processing time of the color development process for these two types of light-sensitive materials with different total coated silver amounts may be the same or different, but 1. Normally, the processing time for light-sensitive materials with a small coated silver amount is shorter. and processed.

The replenishment amount of the color developing solution according to the present invention is 1. In the case of a photosensitive material having a total coated silver amount of 2 g/m2 to 10 g/m,
The effect of the present invention is better exhibited when the photosensitive material has 10+s to 900a+ patterns per rn', and especially when the photosensitive material has 20 layers to 900a+ patterns.
The effects of the present invention can be favorably obtained in the range of 700 meters, particularly in the range of 30 meters to 500 meters. Furthermore, in the case of the photosensitive material of the present invention with a total coated silver amount of 1 g/m2 or less,
The effect of the present invention is better exhibited when the photosensitive material is 10 m to 400 m, and especially when the photosensitive material is 20 m to 20 m
The effects of the present invention can be favorably obtained in the range of 0, particularly in the range of 3011 to loO+s.

In the present invention, usually after color development processing, processing is performed with a processing solution having bleaching ability.

A metal complex salt of an organic acid is used as the bleaching agent used in the bleaching solution or bleach-fixing solution used as the processing solution having bleaching ability, and the metal complex salt oxidizes the metal salt generated by development. It has the effect of converting it into silver oxide, and its composition is a complex formed with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid with a metal ion such as iron, cobalt, or copper. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these organic acids include the following.

(1) Ethylenediaminetetraacetic acid (2) Diethylenetriaminepentaacetic acid (3) Ethylenediamine-N-(β-oxyethyl)-N, N', N'
-) diacetic acid (4) 1.3-propylenediaminetetraacetic acid (5)
Nitrilotriacetic acid (6) Cyclohexanediaminetetraacetic acid (7) Iminodiacetic acid (8) Dihydroxyethylglycine citric acid (9) Ethyl ether diamine tetraacetic acid (10) Glycol ether diamine tetraacetic acid (11) Ethylene diamine tetrapropionic acid (+2) Phenylene Among the ferric salts of the aminopolycarboxylic acids mentioned above, the organic acids preferably used include (1), (2), (4), (
10), especially (1), (2), and (4).

The bleaching solution or bleach-fixing solution used contains the above-described metal complex salt of an organic acid as a bleaching agent, and may also contain various additives. Additives include in particular alkali halides or ammonium halides, rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, metal salts, chelating agents, nitrates and the commonly known bleach accelerators. It is desirable to add pH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions as appropriate. Can be added.

As the fixing agent used in the fixing solution or bleach-fixing solution, all kinds of fixing agents can be used. Examples include thiosulfate or thiocyanate or a combination of thiosulfate and thiocyanate, but there are no particular limitations. It's not a translation,
When thiosulfate is used, the amount added is at least 0.
4 mol/i is preferred, and if thiocyanate is used, the amount added is preferably at least 0.5 mol/i.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide,
A pH buffer agent consisting of various salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination.

In the present invention, in order to increase the activity of the bleach solution or bleach-fix solution, air or oxygen may be blown into the bleach bath or bleach-fix bath and the bleach replenisher solution or bleach-fix replenisher storage tank, if desired. Alternatively, an appropriate oxidizing agent such as hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate, or a material with good oxygen permeability, such as a silicone tube, may be placed in the circulation path to reduce airage. There are also ways to increase the impact.

The pH of the bleaching solution used in the present invention is usually 2.5 to 6.
5, and in the present invention, preferably 3.0 to 5.
It is 5.

The pH of the fixer or bleach-fixer used in the present invention is usually 5.0 to 9.0, preferably 5.5 to 8.5.

In the processing method of the present invention, after color development processing, bleaching and fixing (or bleach-fixing) processing, stabilization processing can be performed without washing with water, or washing processing with water and then stabilization processing may be performed, but preferably In addition to the 0 or more steps in which immediate stabilizing treatment brings out the effects of the present invention, there are also steps such as dura mater, neutralization,
Typical examples of preferred processing methods include the following steps, in which known auxiliary steps may be added as necessary, such as black-and-white development, reversal, and washing with a small amount of water.

Round-ni-row-field"゛ku-1-same charge-side-kuji"'? ” ? In the above, the solid line means the processing flow of the photosensitive material (A) in which the total amount of coated silver of the present invention is 2 g/G to 10 g/112, and the broken line indicates the process flow of the photosensitive material (A) whose total coated silver amount is 1 to 1. gor
It means the processing flow of the photosensitive material (B) below r1'.

Among these steps, especially (1) and (2).

Step (3) is preferably used.

Another preferred embodiment of the processing method of the present invention is a method in which part or all of the overflow solution of the color developing solution flows into the subsequent step of bleaching solution or whitening solution. In addition, when a color developer is allowed to flow into the bleach or bleach-fix solution at a constant rate, the generation of sludge in the bleach or bleach-fix solution can be suppressed, and surprisingly, silver recovery from the bleach-fix solution can be suppressed. The effect is also improved.

Furthermore, in addition to the above-mentioned method, when part or all of the stabilizer solution or overflow solution according to the present invention is poured into the bleach-fix solution or the fix solution, the above-mentioned effects can be obtained. Plays well.

Furthermore, it is also a preferred embodiment of the present invention to flow part or all of the bleaching solution or fixing solution from the processing tank for high-silver content photosensitive materials into the processing tank for low-silver content photosensitive materials. The effect is better.

Examples of the processing solution used in the processing of the present invention include a color developing solution, a bleaching solution, a bleach-fixing solution, a fixing solution, a stabilizing solution, a black-and-white developer, a stop solution, a rinsing solution, and a hardening solution. Regarding bleaching solutions, see JP-A No. 2-44347, pages (3) to (4).
) and JP-A-2-43546, pages (37) to (38), conventional additives such as bleaching agents, amounts of pH 1 acids and chain acids, and bleaching accelerators are used, and further fixing As for the liquid, usual additives such as a fixing agent, a fixing accelerator, a preservative, a chelating agent, etc. described in JP-A No. 2-44347, page (4) can be used. As a bleach-fixing solution, JP-A No. 2-43548, pages (37) to (3)
8) is used. Furthermore, the stabilizer according to the present invention includes bactericidal agents, anti-piping agents, chelating agents, surfactants, optical brighteners, etc. described in JP-A-2-43548, pages (38) to (39). is used.

The replenishment amount of the bleach, bleach-fix and fixing solutions is usually 501 to 900 per weight of the light-sensitive material, preferably 1 when the total coated silver amount is 2 g/m2 or more.
00■l to 500■l, and the total coated silver amount is Ig.
/m2 or less, 10 to 400 square meters per rn' of the photographic material is usually used, preferably 2 cm2 or less.
The range is 0■J1 to 100 recommendations.

Next, preferred photosensitive materials to which the present invention is applied will be explained.

The silver halide grains used in photosensitive materials include silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide, but the amount of silver is 2.
g to 10 g/m' of photosensitive material (A) preferably contains at least 1 mol% of silver iodide, particularly preferably an iodine containing 2 mol% to 30 mol% of silver iodide. Silveride emulsions are preferred, such as those disclosed in JP-A-2-190
Examples include high iodine-containing photosensitive materials as disclosed in Japanese Patent No. 854 and Japanese Patent No. 2-190855.

The light-sensitive material (B) with a silver content of 1 g/m' or less preferably uses silver chloride or silver chlorobromide, and preferably contains silver chloride in a high concentration, for example, 50 mol% or more of silver chloride. .

The high concentration silver chloride emulsion will be explained below.

The silver halide grains preferably used in photosensitive materials are silver halide grains mainly composed of silver chloride containing at least 50 mol% or more of silver chloride, more preferably 80 mol% or more, and even more preferably 90 mol% or more. What it contains;
Particularly preferably, the content is 95 mol% or more, and most preferably 88 mol% or more.

The silver halide emulsion mainly composed of silver chloride may contain silver bromide and/or silver iodide as a silver halide composition in addition to silver chloride. In this case, silver bromide is preferably 20 mol% or less, More preferably 10 mol% or less, still more preferably 3 mol% or less, and when silver iodide is present, 1 mol% or less is preferable, more preferably 0.5 mol% or less,
Most preferably it is zero. Such silver halide grains consisting mainly of silver chloride containing 50 mol% or more of silver chloride may be applied to at least one silver halide emulsion layer, but are preferably applied to all photosensitive silver halide emulsion layers. It is to be applied.

The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [1,O,O] planes to [1,1,1] planes can be used.

Furthermore, the crystal structure of these silver halide grains.

These silver halides may be uniform from the inside to the outside, or may have a layered (phase) structure (core-shell type) with different inside and outside parts. It may be a type that is mainly formed on the surface or a type that is formed inside the particle.

In addition, tabular silver halide grains (JP-A-58-1139
No. 34 and Japanese Patent Application No. 170070/1983) may also be used. Also, JP-A-84-28837, JP-A No. 84-28837,
Silver halides described in No. 288'18, No. 64-77047, etc. can 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.

For example, when growing silver halide grains, p) 1. It is preferable to control PAg and the like, and to sequentially and simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains as described in, for example, JP-A No. 54-48521.

The silver halide emulsion layer of the light-sensitive material processed according to the invention contains color couplers. These color couplers react with color developer oxidation products to form non-diffusible dyes. Color couplers are advantageously incorporated in non-diffusive form in or closely adjacent to the photosensitive layer.

Thus, the red-sensitive layer may contain, for example, a non-diffusive color coupler, generally a phenolic or alpha-naphthol coupler, which produces a cyan partial color image.

The green-sensitive layer may contain, for example, at least one non-diffusive color coupler which produces a magenta partial color image, usually a 5-pyrazolone color coupler and a pyrazolotriazole. The blue-sensitive layer may contain, for example, at least one non-diffusive color coupler that produces a yellow color image, generally a color coupler having open-chain ketomethylene groups. Color couplers can be, for example, 6.4 or 2 equivalent couplers.

In the present invention, 2-equivalent couplers are particularly preferred.

Suitable couplers are disclosed, for example, in the following publications:
Agfa research report (Mitteilunglnaus)
den Forschungslaboratory
der Agfa).

Leverkusen/Munich
n/Muncben), Vol, IIl, p, 1
11 (19G1) Medium Double Velvet (W, Pe1z
"Color coupler" by Farbkupler
); Kay Ventakataraman (K.

Venkatara+wan), “The Chemistry
Of Synthetic Soybeans (The Che
mirsr2 ofSynthetic [)yes)
, Vol. 4.341-387. Academic Press, “The Theory
Of the Φ Photographic Process J (The
Theory of the Photography
c Process), 4th edition, pp. 353-362; and Research ψ Disclosure.
[]1sclosure) No. 17843, Section ■.

In the present invention, in particular, JP-A-63-106655
General formula [M-1] as described in the specification, page 26
Magenta couplers shown in (Specific examples of these magenta couplers include No. 1-No. 77 described in JP-A-63-108855, pages 29 to 34); The general formula [C
-I] or [C-III (specific examples of cyan couplers include the same specification, 37-4
(c'-i) to (C'-82), (C''-
1) to (C″-38)), high-speed yellow couplers described on page 20 of the same specification (specific examples of cyan couplers include (Y
'-1) to (Y'-39)) are preferably used from the viewpoint of the desired effects of the present invention.

In the present invention, the intended effects of the present invention are better achieved especially when a magenta coupler represented by the general formula (M-r) is used.

In the magenta coupler represented by the general formula CM-I) N-N・-1・, 2 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z is a substituent. It may have.

Alternatively, it represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typically includes six groups such as alkyl, aryl, anilino, anrulamino, sulfonamide, alkylthio, arylthio, alkenyl, and ncroalkyl. Atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, nitrogenroxy, acyloxy/
, carbamoyloxy, amine, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, as well as spiro compound residues, bridged Also included are hydrocarbon compound residues and the like.

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

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

Examples of the anrulamino group represented by R include alkylcarbonylamino groups, arylcarbonylamino groups, and the like.

Examples of the sulponamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

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

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

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

Examples of the sulfonyl group represented by R include an alkylsulfonyl group and an arylsulfonyl group.

Examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group.

Phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloki/phosphonyl groups, arylphosphonyl groups, etc.; acyl groups include alkylcarbonyl groups, arylcarbonyl groups, etc.; carbamoyl groups include alkylcarbamoyl groups and arylcarbamoyl groups. etc.

As the sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl groups, etc.; examples of acyloxy groups include alkylcarbonyl groups, arylsulfamoyl groups, etc.

Examples of the carbamoyloxy group include an alkylcarbamoyloxy group and an arylcarbamoyloxy group.

Examples of the ureido group include an alkylureido group and an arylureido group.

Examples of the sulfamoylamino group include an alkylsulfamoylamino group and a 7-arylsulfamoylamino group; as the heterocyclic group, a 5- to 7-membered group is preferable; specifically, a 2-furyl group, a 2-thienyl group, etc. , 2-pyrimidinyl group, 2-benzothiazolyl group, etc.

The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, such as 3,4,5.6-tetrahydropyranyl-2-oxy group, l-phenyltetrazole-5-
Oxy/Group etc.: As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5- Nialoxy groups such as triazole-6 monothio group include trimethylsiloquine group, triethylsiloquino group, dimethylbutylnroquine group, etc. Imide groups include succinimide group, 3-hebutadenesuccinimide group, phthalimide group, glutarimide group. Groups, etc.; spiro compound residues include spiro [331heptane-
1-il et al.

As a bridged hydrocarbon compound residue, bicyclo [22,1
1 hebutan-1-yl, tricyclo [3,3,1,1
Examples include 3.7]decane-■-yl, 7.7-dimethyl-pinchlor[2,2,1]hebutan-1-yl, and the like.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyluoquine, Alfkidicarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkyloxalyloxy,
Alkylthio, arylthio, heterocyclic thio, alkylokinothiocarponylthio, anoralamino, sulfonamide, nitrogen-containing heterocycle bonded by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboquinyl, N-N'・-pa(R1 ' has the same meaning as R, 2' has the same meaning as 2, and R2' and R1' represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group. Preferably it is a /\rogen atom, especially a chlorine atom.

Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned.

More specifically, those represented by the general formula CM-I) are represented by, for example, the following general formulas (M-n) to [M-■].

General formula CM-11) General formula ('M-111) -N-N General formula (M-rV) General formula (M-V) General formula (M-Vl) -N-N General formula (M-113) ~ [M-■] R1-R
1 and X have the same meanings as R and X above.

Also, among the general formulas (M-I), those represented by the following general formula [M-■] are preferred.

General formula [M-■] In the formula, R, , X and Z have the same meanings as R, X and Z in 14-B formula CM-1)i:.

Among the magenta couplers represented by the general formulas (M-I1) to [M-■], particularly preferred ones are those represented by the general formula (M-TI
) is a magenta coupler.

Substituents that the ring formed by Z in general formula CM-I) and the ring formed by Zl in general formula [M-■] may have, and M-
R1-R1 in '/I) is represented by the following general formula [M-
(2) is preferable.

General formula CM-II) -R'-SO, -R' In the formula, R1 represents an alkylene group, and 12 represents an alkyl group, an cycloalkyl group, or an aryl group.

The alkylene group represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and does not matter if the straight chain has 9 branches.

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

In addition, when used for positive image formation, the substituent R on the heterocycle
and R, most preferably the following general formula [M-χ
].

General formula CM-X'I R9 R4゜-〇- 1 History.

In the formula, R,,R,. and R1, each has the same meaning as R above.

Also, the above R,,R,. and two of R11, for example R1
and R1° may be combined to form a saturated or unsaturated ring (e.g., nochloroalkane, cycloalkene, heterocycle), and furthermore, R1, may be combined with the chain ring to form a bridged hydrocarbon compound residue. It's okay.

Among the general formulas CM-X), (i) R, ~
When at least two of R++'q are alkyl groups, (
u) One of R+ to R11, for example, R11, is a hydrogen atom, and the other two, R1 and R3°, combine to form a cycloalkyl with the root carbon.

Furthermore, in (1), it is preferable that two of R1 to R11 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

In addition, when used for negative image formation, the substituent R on the heterocycle
And R3 is most preferably represented by the following general formula (M-1
It is expressed by

General formula (M-XI) R, -CI-1, - In the formula, R12 has the same meaning as R above.

Preferred as R11 is a hydrogen atom or an alkyl group.

Typical specific examples of the compounds according to the present invention are shown below.

l1837 C,H.

Nils’, C.F.

CaH++ Shihko * -C,H,,(1) +11121 Cll+ C+ +H+ 1 113 CH.

57 o.

Take H N -N -N N -N -N and 11th (t) x:y-50:50 x:y-50:50 x:y-50:50 Representative of the above compounds according to the present invention In addition to specific examples, specific examples of compounds according to the present invention include JP-A-62-1663.
Among the compounds described on pages (18) to (32) of Specification No. 39, No. 1 to 4, 6.8 to 17.19 to
24.26-43.45-59.61-104.106
-121.123-162.164-223 can be mentioned.

Also, the coupler is described in the Journal of the Chemical
Society (Journal o(the Cheo)
+1calSociety), Perki
n) I (1977), 2047-2052, U.S. Special Pestle No. 3.725.067, Japanese Unexamined Patent Publication No. 1983-'19437
No. 511-42045, Fl 59-16254
No. 8, No. 59-171956, l5160-3355
It can be synthesized by referring to No. 2, No. 60-43659, No. 60-172982, No. 60-190779, No. 62-209457, No. 63-307453, etc.

The couplers of this invention typically have I/mole of silver halide.
X 10-' mole, preferably l X 10-'
It can be used in the range of 1.5 molar to 8.times.10 molar.

The couplers of the present invention can also be used in combination with other types of magenta couplers.

Further, the total coating silver amount of the present invention is 2 g/rrr' to IOg
/m2 of the photosensitive material is preferably in the range of 3 to 10 g/m', more preferably in the range of 4 to 9 g/m2. Furthermore, the photosensitive material of the present invention having a total coated silver amount of 1 g/rrf or less is preferably in the range of 0.2 to 0.9 g/m', more preferably 0.3 to 0.7 g/m' is within the range of

When a nitrogen-containing heterocyclic mercapto compound is used in a light-sensitive material containing a silver chloride-based emulsion, it not only exhibits the desired effects of the present invention well, but also prevents oxidation when a bleach-fix solution is mixed into a one-color developer. This can be cited as a more preferred embodiment of the present invention because it has the additional effect of making the resulting influence on photographic performance extremely slight.

Specific examples of these nitrogen-containing heterocyclic mercapto compounds include (I'-1) to (I'-87) described in JP-A-83-108655, pages 42 to 45.

The silver halide emulsions may be prepared by conventional methods (eg, single or double flow with constant or accelerated flow of material). Particularly preferred is the adjustment method using the double inflow method with pAg t-adjustment; Research Disclosure N
o, 17643, see Sections I and ■.

Silver halide emulsions can be chemically sensitized. Reducing agents can also be used as chemical sensitizers, with sulfur-containing compounds such as allyl isothiocyanate, allylthiourea or thiosulfate being particularly preferred;
, 887; and polyamine or amine methyl sulfinic acid derivatives, such as diethylenetriamine according to Belky Patent No. 547,323. Noble metals and precious metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitization method is described in the Zeitschrift Fair Book Bissenschaftliche Fotograf 4.
(Z, Wiss, Photo,) 4B, 85-7
2 (1951) by R. Koslovsky (R, Kos
iovsky); see also Research Disclosure No. 17843, Section 2 above.

Silver halide emulsions are prepared by optically known methods, for example using common polymethine dyes such as dinitrodianes, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oquinol and the like.
It can be sensitized. F.M. Hammer (F,
M, l (amer)'s ``Cyanine Dice &amp;
Relay Chit Combines J (The Cyan
ine Dyes and relatedCo+5p
ounds) (1954) Ullmann's Hemy (lJI)
Imanns Enzyklpadie der tec
hnischen Chemie) 4th edition, vol. 18, 4
See page 31 and the following, and Research Disclosure No. 17643, above, Section ■.

Conventional antifogging agents and stabilizers may be used in silver halide emulsions. Azaindenes are particularly suitable stabilizers, with tetra- and penta-azaindenes being preferred, especially those substituted with hydroxyl or amino groups.

Compounds of this type are described, for example, in the paper by Birr.

Zeitschrift Fuyur φ Bissenschaft Liche Φ Photograph 4 (Z, Wiss, Photo
) 47° 1952, P, 2-58, and the above-mentioned Research Disclosure No. 17643, Section 2.

Components of the photosensitive material can be incorporated by conventional known methods; for example, U.S. Pat. No. 2,322,027, U.S. Pat.
3.764,336 and 3.71 (see No. 5,897).

Components of the photosensitive material, such as couplers and UV absorbers, can also be included in the form of charged latex;
Components can also be immobilized in light-sensitive materials as polymers; see, for example, US Pat. No. 2,044,992, US Pat. .370. ! 35
See No. 2 and No. 4,080,211.

As a support for the light-sensitive material, conventional supports can be used, for example supports of cellulose esters such as cellulose acetate and supports of polyesters.
Reflective supports such as paper supports can also be used in the present invention, and these include, for example, polyolefins,
In particular it can be coated with polyethylene or polypropylene; in this regard Research Disclosure No. 17643, Section VV? reference.

In the present invention, when a vinyl sulfone type hardener is used in the photosensitive material, the effects of the present invention are better exhibited.

A vinyl sulfone hardener is a compound that softens a vinyl group bonded to a sulfonyl group or a group capable of forming a vinyl group, and preferably a vinyl group bonded to a sulfonyl group or a group capable of forming a vinyl group. It has at least two.

For example, a compound represented by the following general formula [VS-I] is preferably used in the present invention.

General formula [VS-I] L-(S02-X) layer In the above general formula [VS-I], shi is a linking group of cabinet value, and X 1f-C'thCH2t ta is 1082C
H2Yte is present, and Y represents a group that can be eliminated in the form of HY with a base, such as evaporation, a halogen atom, a sulfonyloxy group, a sulfoxy group (including salts), a tertiary amine residue, etc.

■ represents an integer from 2 to 1O, but when m is 2 or more, -5O
2-X may be the same or different from each other.

The m-valent linking group is, for example, an aliphatic hydrocarbon group (e.g.
Alkylene, alkylidene, alkylidine, etc. or
groups formed by combining these), aromatic hydrocarbon groups (
For example, arylene (or a group formed by combining these), -0-.

-NR- (R' is a hydrogen atom or preferably has 1 to 1 carbon atoms
(represents 15 alkyl groups), -s-, -x-, -c
o, -5o-.

It is a base formed by combining one or more bonds represented by -802- or -9O3-, and when it contains two or more -NR'-, those R's are bonded together. The linking group which may form a ring further includes those having a substituent such as a hydroxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group or an aryl group.

Specific examples of X include -CH=CH2 or -CH2C
H2C1 etc. are preferred.

Typical examples of vinyl sulfone hardeners are shown below.

Margin below VS-11+2c=cH3o2CH3SO2CH-CH
2S-28,C=CI(S02(C1(2),502C
l(-C:)12VS-3H2C-CH302(C11
2) 3SO, C11-(:+12VS-4H2C=CH
302CI+20C112SO, C11-CH.

■S-5) 12C=C11302 (CIl 2) 20
(C112) 2So 2C8-C11°VS-6H2
C=CN302 mountain g:cl12s02CIl=C112
VS-882C=CIISO, C112CON11C1
12811(:OC+1.5O2CII=CI12VS
-'l 11. C-Cl+5(12C112CON+
1 (C11,), N11C (lc1+2sO2cll-
CIl.

VS-10 82C-CIlSO2C112CONlIC112C1
12C112NllCOC112SO□C11-CI1
2COCII, So, Cl1=C11゜吃VS-+a VS-14)12C=CH302(CIl2)2CON
H-CH2H association C-CH5O2 (CH□)2CONII
-CH.

MS-15c, H.

N3)1. c-CH9O,CH2' CI(,S
O, (:H-C1l.

VS-20 [(H,C-t':H3O2)JCCH,S
O, (CHI)2SCH2], COS-21 VS-22 ()I2CJ:)IsO,CH,), CVS
24 (H2C=CH3O2CH2)rCc2HsC
H! =CH3O! 'N''SOIC)l=cH1VS-3
0H2C1-CH5Oz(CH2)2SOz(CH2)
2SO□CH=CH2VS-31 HC=CH3O2(CHa)20(CH2)JHON
H(C1la)to-(CI(2) 2SO,CH=C
H.

H,C=CH3O,CH2 VS-35(H,C=CH3O2NH)2CH2S-3
6 82C=C11302(C)12)2NH(CI+2)
28H(CH2)2SO2CH=CH2VS-37(H
, C-Cll5O, (CH,), C0NC112)2C
H.

L VS-:18 VS-39 VS-41G, H,, C (CH2SO2CH-CH2)
:+VSi4 G)12(CON)IC)12so
2CH=C112)2VS-46C[C0(CH,),
SO, CH=C)12].

VS-48NH [(c12so2cH=c++2]2V
S-49CH,C(C)I20CH2SO,CH=CH
2):1VS-50C(CH20CH2SO2CH-C
H2).

VS-51N[(CH2)20C)12sO,cH=c
H, ]3VS-52 (CH2=CH3O2CH2), C
CH302(CH,)2C sentence VS-53H2C=CH3
O2C1l=C11°VS-57 The vinyl sulfone hardener used in the present invention is, for example, an aromatic hardener as described in US Pat. Compounds, Japanese Patent Publication No. 44-29622, No. 47-2537
No. 3, alkyl compounds bonded with hetero atoms as described in Japanese Patent Publication No. 47-24259, etc., Japanese Patent Publication No. 47-8
Sulfonamides and ester compounds as described in No. 736, 1.3', 54 lis [β-(vinylsulfonyl)-propionyl]-hexahythro S as described in JP-A No. 49-24435, etc. -Triazine or Japanese Patent Publication No. 50-35807, Japanese Patent Publication No. 51-44
It includes alkyl compounds such as those described in JP-A-59-18944 and the like, and compounds described in JP-A-59-18944 and the like.

These vinyl sulfone hardeners are dissolved in water or organic solvents and have a binder (eg, gelatin) of 0.00%.
005-20% by weight, preferably 002-10% by weight
used.

For addition to the photographic layer, a patch method or an in-line addition method is adopted.

The layer to which these hardeners are added to the photographic layer is not particularly limited, and they may be added to, for example, the top layer, the bottom layer, or the entire layer.

Further, in the present invention, it is preferable that the silver halide color photographic light-sensitive material contains at least one of the compounds represented by the following general formulas (B-1) to (B-3).

General Formula [B-1]0M ). R2 and R3 each represent a hydrogen atom, a halogen atom, an amine group, a nitro group, a hydroxyl group, an alkoxycarbonyl group, a carboxylic acid group (including its salts), or a sulfonic acid group (including its salts) 0M represents a hydrogen atom, an alkali Represents a metal or ammonium group] General formula [B-2] General formula [B-3] 1?1 [wherein R4 is a hydrogen atom, a halogen atom, an alkyl group,
Aryl group, halogenated alkyl group, -RI2-OR1
1, -C:0NHR14 (here, R12 represents an alkylene group, R13 and RI4 each represent a hydrogen atom, an alkyl group, and an arylalkyl group), represents an arylalkyl group, and R5 and R6 represent a hydrogen atom and a halogen group, respectively. atom, a halogenated alkyl group, an alkyl group, R7 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogenated alkyl group, an arylalkyl group 1 (15
0R+6゜-〇〇NHRl 7 (where R15 is an alkylene group, R16 and R17 are both a hydrogen atom and an alkyl group), R8, R9, R10, 1lil
+ represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an amide group, or a nitro group; specific examples of compounds represented by the general formula [B-1] include:
The following exemplified compounds may be mentioned.

(B-1-1) (B-1-2) (
B-1-3) (B-1-4) (B
-1-5) (B-+-6) (B-
1-7) ([3-1-8) (B-
1-9)' (B-1-10)(
B-1-11) (B-i-12
)NH7 (B-1-i3) ([(-1-
11) Oll'
0H(B-1-Is) (B
-1-16) (B-1-17)
(B-1-18) NH.

(B-1-19:1H The compound represented by the above general formula [B-1] is known as a preservative for mandarin oranges, etc., and some are commercially available, and those skilled in the art can easily obtain them. be able to.

Among the above exemplary compounds, preferred compounds are [B-1
-1], [B-1-2, [B-1-
3], [B-1-4] and [B-1-5].

The compound of general formula [B-1] used in the present invention is 1
It is preferable to use the stabilizer of the present invention in an amount of 0.03 to 50 g per exchange, more preferably 0.12 to log;
Particularly preferably 0.15 to 5 g.

Specific examples of the compounds represented by the general formulas [B-2] and [B-3] are described below, but the invention is not limited thereto.

[B-2-1,]]2-methyl-4-inthiazoline 3
=one [B-2-2] 5-chloro-2-methyl-4-thiazolin-3-one [B-2-3] 2-methyl-5-phenyl-4-thiazolin-3-one [ E-2-4]4-bromo5-chloro-2-methyl-
4-inchararin-3-one [B-2-5]2-hydroxymethyl-4-inchararin-3-one [B-2-6co2-(2-ethoxyethyl)-4-incharazoline -3-one[J3-2-7]2-(N-methyl-carbamoyl)-
4-Isothiacillin-3-one [B-2-8]5-bromomethyl-2-(N-dichlorophenyl-carbamoyl)-4-thiaralin-3-one [B-2-9co5-chloro-2- (2-phenylethyl)-4-thiaralin-3-one [E -2-10co4-methyl-2-(3,4-dichlorophenyl)-4-isothiazolin-3-one [B-3-1 ]1.2-benzithiazolin-3-one [E-3-2co2-(2-bromoethyl)-1,2-benzisothiazolin-3-one [B-3-3]2-methyl-1, 2-benzisothiazolin-3-one [B-3-4] 2-ethyl-5-nitro 1,2-benzisothiazolin-3-one [B-3-5] 2-hensyl-1,2- Penzinthiazorin-3-one [B-3-6]5-chloro-1,2-henzinthiathrin-3-one These exemplary compounds are described in U.S. Patent No. 2,787,172, U.S. Pat. No. 2,767.173, U.S. Patent No. 2,767.174, U.S. Patent No. 2,8
Synthesis methods and examples of applications in other fields are described in Patent No. 70,015, British Patent No. 848,130, French Patent No. 1,555,418, etc. There are also commercially available products such as Topside I"300 (Permakem Asia ■), Topside 600 (Permakem Asia■), Finesight J-700 (Tokyo Fine Chemical 1!I3), Proxel GXL (1,
C:, 1. ■) It is possible to obtain it under the product name.

The compounds represented by these general formulas (B-1) to (B-3) are O, 1mg-500+ag per 1 m' of photosensitive material.
(7) Used in the range of 0.5 mg to 1
Used in the range 00a+H. Also, these [:B-
Two or more of the compounds represented by 1) to (B-3) may be used in combination.

In the present invention, the photosensitive material may include color paper, color negative film, color positive film, color reversal film for slides, and color film for movies, as long as it is a photosensitive material that contains a coupler and is processed by the so-called internal development method. It can be applied to any two types of photosensitive materials such as reversal film, color reversal film for TV, and reversal color paper, but most preferably, color paper is used as the photosensitive material (B) and color negative film is used as the photosensitive material (A). That's true.

[Effects of the Invention] According to the present invention, it is possible to process photosensitive materials with different amounts of silver in a common tank or a common replenisher, the generation of sludge and scum in the stabilizing tank is suppressed, and the Provided is a method for processing silver halide color photographic materials, which prevents the occurrence of yellow stain and fading of magenta dyes due to storage of color negative films, and suppresses dark fading of cyan dyes due to storage of color paper after color processing. can do.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by these Examples.

Example 1 Preparation of color paper sample> Each layer of the following composition was coated on a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the first layer side of the other side. Then, the following multilayer silver halide color photographic material was prepared. The coating solution was prepared as follows.

1st layer coating liquid Yea-coupler (Y-1) 2G, 7g, dye image stabilizer (ST-1) 10.0g, (ST-2) 6.
87g of additive (HQ-1), 7g of fi are dissolved in 6.5g of high boiling point organic solvent (DNP) by adding 60mM of ethyl acetate, and this solution is mixed with 7mM of 20% surfactant (SU-1).
A yellow coupler dispersion was prepared by emulsifying and dispersing a 10% gelatin aqueous solution containing 220 fat using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions.
A layer coating solution was prepared.

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

In addition, (H-1) was added to the second layer and the fourth N as a hardening agent.
(H-2) was added to the seventh layer. As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension.

Y-1 QC) 13 M-2CC D0P Nooctylphthale-1・l) N
P Tsunonyl phthalate DIDP Diisodenol phthalate PVP Polyhinyl virolitonol-
1 ST-I S'r-23T
-35T-11 0C,H.

5LI-I 5U-2StJ
-3 CH, C00C)! ! (CF, CFI), HCHCOO
CR2 (CF, CF, ), ) 10Ja H-I H-2,, ONa [Preparation method of blue-sensitive silver halide emulsion] 1000 ml of 2% gelatin aqueous solution kept at 40°C The following (liquid A) and ( B solution) was added simultaneously over 30 minutes while controlling the pAg to -8,5, p) l-3,0, and the following (C solution) and (
Solution D) at pAg=7.3. They were simultaneously added over 180 minutes while controlling the pH to 5.5.

At this time, pag was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Liquid A) Sodium chloride 3.42g Potassium bromide 0.03g Add water
200 measurements (liquid B) Add 10g of silver nitrate water
20011J1 (Liquid C) Sodium chloride 102.7g Potassium bromide 1.0g Add water
Add 600g of silver nitrate (solution D) and 300g of water.
After adding 600ff1, add 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and magnesium sulfate.
After desalting using a 0% aqueous solution, it is mixed with a gelatin aqueous solution and the average particle size is 0.85 m, coefficient of variation (σ/r) =
A monodisperse cubic emulsion EMP-1 having a silver chloride content of 99.5 mol% was obtained.

The above emulsion EMP-1 was heated at 50°C using the following compound.
Chemical ripening was carried out for 90 minutes at , to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8+g1 mol Ag
X Chloroauric acid
0.51℃g1mol AgX stabilizer Scho AB
-56X l0=El/Eh AgX sensitizing dye BS
-14X 10-'th/moh AgXB5- 2
1 X 10-'i#:6 ag
x [Method for preparing green-sensitive silver halide emulsion] (Liquid A) and (
The average particle size was 0 in the same manner as 1tEMP-1 except that the addition time of B liquid) and the addition time of (C liquid) and (D liquid) were changed.
．． 43 g wr , coefficient of variation (σ/r) = 0.08,
Monodispersed cubic emulsion EMP with silver chloride content of 99.5 mol%
-2 was obtained.

E) For IP-2, use the following compound at 55°C for 12
A green-sensitive silver halide emulsion (Em-
G) was obtained.

Sodium thiosulfate 1.5 g 1 mol Ag
X Chloroauric acid 1.0 g/moh
AgX stabilizer 5TAB-1jX 10-'es/v:
s AgX sensitizing dye GS-14X 10-'moh
/eh AgX [Preparation method of red-sensitive silver halide emulsion] Same as EMP-1 except for changing the addition time of (Liquid A) and (Liquid B) and the addition time of (Liquid C) and (Liquid D). , average particle size O, 5 OuL intestine, coefficient of variation (σ/r) =
0.08. Silver chloride content! A monodispersed cubic emulsion EMP-3 containing 3L and 5 mol % was obtained.

EMP-3 was chemically ripened at 60°C for 80 minutes using the following compound to form a red-sensitive silver halide emulsion (Em-R).
I got it.

Sodium thiosulfate 1.8g/mo, A
gX Chloroauric acid 2.0 g 1 mol AgX stabilizer 5TAB-16X 10-4 mol 1 mol agx sensitizing dye RS-11X IO"+s
/Mos AgXS-1 S-2 S-1 S-1 TAB-1 Of the color paper samples created in this way! The amount of silver coated on the second coat was 0.58 g/m'. The total amount of coated silver was varied as shown in Table 1 below, and experimental color paper samples were prepared and used.

Preparation of color negative film sample> In all the examples below, the amount added in the silver halide photographic light-sensitive material is expressed in grams per ml unless otherwise specified. Colloidal silver is expressed in terms of silver. Sensitizing dyes are expressed in moles per mole of silver. - On a triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare a multilayer color photographic material sample 1.

Sample-1 1st layer; Antihalation layer (HC) Black colloidal silver 0.1 IUV absorber (UV-1) "0.18 Caranidocyan coupler (C'C-1)" 0.02 High boiling point solvent (Oil -1) 0.18tt
-(Oil-2) ' 0.20 Gelatin +Js 2nd calendar; Intermediate layer (IL-1) Gelatin 1/2 3rd layer;
Low-sensitivity red-sensitive emulsion layer (R-L) Silver iodobromide emulsion (silver iodide 3
Mol%) 0.75 Sensitizing dye (S-1)
3.2X 1O-4 (Moh/1 mole of silver)// (
S2) 3.2XIO=(tt-)tt
(S-3) 0,2X”1O-4(//
) Cyan coupler (C-1) ” ” 0
．． 45tt (C-2)' 0.1
5 colored cyan coupler (CC-1) 0.
07DIR compound (D-1)' 0.
001tt' (D-2) 0.
01 High boiling point solvent (Oil-1) 0.
5 Gelatin 1.0 4th layer; High sensitivity red-sensitive emulsion layer (R-H) Silver iodobromide emulsion (silver iodide 7 mol%) 0.75 Sensitizing dye (S -1)
1.5X 1O-4 (mol/1 moh silver)”
(S-2) 1.6Xlo-'(tt)t
t (S -3) 0. lX10-'(//
) Cyan coupler (C-2) 0.
22 colored cyan coupler (CC-1) 0
．． ．． 03DIR compound (D-2) 0.
02 High boiling point solvent (Oil-1) 0.
24 Gelatin ]・0 No. 5
Layer: Intermediate layer (IL-2) Gelatin 1.0 6th N:
: Low-sensitivity green-sensitive emulsion layer (GL), silver iodobromide emulsion (silver iodide 4 mol%) 0.8 sensitizing dye (S-4) 7
．． OX 1O-4 (mol/silver 1 mol)// (S-
5) 0.8X10-4 (// ) Magenta coupler (M-1) 0.17tt
(M-2) 0.43 colored magenta coupler (GM-1) 0.10 DIR compound (D-3
) 0.02 high boiling point solvent (Oil-2)
0.58 gelatin
1.1 Seventh calendar; Highly sensitive green-sensitive emulsion layer (G
-H) Silver iodobromide emulsion (silver iodide 8 mol %) 0.8 sensitizing dye (S -6) 1. IX 1O-4 (mol/silver 1
mole) // (S-7) 2.0X10-4
(// )// (S-8) 0.3X
10-4 (/I) Magenta coupler (M-1)
O, Q3// (M -2)
0.13 colored magenta coupler (GM-1) 0.04 DIR compound (D-3)
0,00G high clear point solvent (Oil2)
0.35 gelatin
0.9 8th layer; yellow filter layer (y
c) Yellow colloidal silver 0.1 additive (I(S-1) 0.07//
(H3-2) 0.07//
(SC-1) 0.12 high boiling point molten t
s(Oil-2) 0.15 Gelatin 1.0 9th N; Low sensitivity blue-sensitive emulsion layer (B-L) Silver iodobromide emulsion (silver iodide 6 mol%
)0.5 sensitizing dye (S-9) 5.8X 1O
-4 (mol/silver 1 mol) yellow coupler (Y-1)
0.58/l (Y-2)
0.34DIR compound (D-1)
0.003tt (D2)
0.006 High purity point solution M (Oil-2)
0.18 gelatin
1.2 10th layer: High sensitivity blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (silver iodide 12 mol%) 0.5 sensitizing dye (S
-10) 3. OX 1O-4 (mol/silver 1 mol)” (S -11) 1.2X 1O-
4(tt, ) Yellow coupler (Y-1)
0. +8tt (Y-2)
0.10 high clear point solvent (Oil-2)
0.05 gelatin
1.01g 11 layers; 1st protective layer (PRO-1) Silver iodobromide emulsion (fine grains) 0.3 Ultraviolet absorber (UV-1) 0.07/l
(UV-2) 0.1 additive (H
3'-1) 0.2// (H3
-2) Q, 1 high boiling point solvent (Oil
-1) 0.07/l (Oil
-3) 0.07 gelatin
0.8 12N; second protective layer (PR
O-2) Alkali-soluble matting agent (average particle size 2 m) 0.13 polymethyl methacrylate (for average particle size 3) 0.02 gelatin 0.5 In addition, each layer contains the above composition. In addition, coating aid 5U-2, dispersion aid SU-
1. Hardener H-1°H-2 and dyes Al-1 and Al-2 were added as appropriate.

Further, the emulsion used in the above sample was as described in Clothing 1 below. Both are monodisperse emulsions.

Further, the total coated silver amount (each emulsion! f! total) of the color negative film sample prepared in this manner was 4.5 g/g.

As shown in Figure 1 below, the total amount of coated silver was varied, and the amount of coated silver in each emulsion layer at this time was the same as the total coated silver amount 4.
Experimental samples were prepared by varying the total amount of silver coated on each layer of a 50 g/m2 color negative film sample so that the amount and ratio of silver coated on each layer was the same.

UV-10M c, He(t) C+++a S-/I 85 C, H, C, L MS-1 113-2+-
1 1 0 88 ((CH,=C)ISO.CH.). CCH, SQ. (
CH. ), ), 11 (cHJtsoax SIJ-1 (Fluka/-L XC), Stj-
2C-1 Oil - 1 0il
-2C. l+.

Oil-3 A I-1 I-2 SOiK After exposing the obtained color paper to SO3 according to a conventional method, a running treatment was performed according to the following processing steps.

*The first to third stabilization tanks are counter current type, and the replenisher was added to the third tank.

Further, the obtained color negative film sample was processed in accordance with a conventional method using the primary processing conditions and processing solution after exposure. however! 1. White liquor, fixer, and stabilizer were used in the same tanks as those used for color paper.

(Color negative film processing) (The replenishment amount is the value per 1 ml of photosensitive material.) However,
The stabilization process was carried out using a three-tank countercurrent system, in which the stabilizing liquid was replenished into the final tank, and Ohe-Flow was introduced into the previous tank.

λ Blood Disaster (for color paper) Triethanolamine 10g Diethylene glycol 5g N,N-diethylhydroxylamine 3.0g Potassium bromide
20IIIg potassium chloride
2.2g diethylenetriaminepentaacetic acid 5g potassium sulfite 0.2g color developing agent (3-methyl-4-amineamidoethyl)-aniline sulfate) 8.0g potassium carbonate
25g potassium bicarbonate
Add 5 g of water to bring the total volume to 1 sentence, and adjust the pH to 10.10 with potassium hydroxide or sulfuric acid.

λ color disaster! Kobi 1 (for color paper) ゛ Triethanolamine 14.0
g diethylene glycol 8.0gN,
N-diethylhydroxylamine 4.0g Potassium bromide 8+wg diethylenetriamine pentavinegar #100 total 7.5g Potassium sulfite 0.3g (amidoethyl)-aniline sulfate) 12g Potassium carbonate
30g potassium bicarbonate
Add 1g of water to make one sentence, potassium hydroxide or! Adjust to PHto-so with #.

Color development tank solution (for color negative film) Diethylenetriamine 100 m 1.0 g Potassium sulfite 4.0 g Potassium bromide
1.3g hydroxylamine sulfate 2.4g methylaniline sulfate
4.2g potassium iodide
2.3+ag potassium carbonate
Add 30 g of wood to make the total volume 1, and adjust to p) + 10.01 with potassium hydroxide or sulfuric acid.

Color developing replenisher (for color negative film) Diethylenetriamine 100 m 1.2 g Potassium sulfite 4.8 g Hydroxylamine sulfate ': a, og Color developing agent 4~(
N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 6.1g Potassium carbonate 30g Potassium bromide
Add 0.5 g of water to bring the total volume to 1, and adjust the pH to 10.07 with potassium hydroxide or sulfuric acid.

The composition of the bleaching solution used is as follows.

1.3-diaminopropanetetraacetic acid ferric ammonium 0.35 mol ethylenediaminetetraacetic acid disodium 2 g ammonium bromide 150 g glacial acetic acid
40mfL ammonium nitrate
Add 40g of water to make one sentence, and adjust the pH to 4.5 using ammonia water or glacial acetic acid.

The composition of the bleach replenisher used is as follows.

1.3-diaminopropanetetraacetic acid ferric ammonium 0.40 mol ethylenediaminetetraacetic acid disodium 2 g ammonium bromide 170 g ammonium nitrate
50g glacial acetic acid
Add F31*+1 water to make one sentence, and adjust to pH 3.5 using aqueous ammonia or glacial acetic acid.

The compositions of the fixer and fixer replenisher used are as follows.

Sodium thiosulfate 50g Potassium thiocyanate 2,0 mol Anhydrous potassium bisulfite 20g Sodium metabisulfite
4.0g ethylenediaminetetraacetic acid disodium Ig Add ice and 1
P) 16.5 using aqueous ammonia or glacial acetic acid.
Adjust to.

The compositions of the stabilizer and stable replenisher used are as follows.

1.2-Hentinthiazolin-3-one 0.1
3C8H17+0-(-OH2CH20+, oH2,0
m-text siloxane (U CC!11!l-78)
O, 1g formaldehyde (37% W/m) or the compound of the present invention The pH listed in Table 1 was adjusted to 8.
5 and add water to make lfL.

The automatic developing machine used has a structure having the processing steps shown in FIG.
A tank force scale system was used.

In Figure 1, la is a color developing tank for color negative film, l
b is a color developing tank for color paper, 2 is a bleaching tank, 3 is a fixing tank, 4 is the first stabilizing tank, 5 is the second stabilizing tank, and 6 is the third stabilizing tank. 7 to 11 are metering pumps for replenishment.

Of the compositions of the above-mentioned stabilizer and stable replenisher, formaldehyde was changed to the compounds shown in Table 1, and a running process was performed using color paper and color negative film prepared.

In the ranking process, the automatic processor is filled with the color developing tank liquids for color paper and color negative film, as well as the bleach tank liquid, fixing tank liquid, and stabilizing tank liquid, and the color paper and color negative film samples are processed. At the same time, the color developing replenisher, bleach-fixing replenisher, and stable replenisher described above were replenished through a metering pump.

Further, the running process was carried out discontinuously until the total amount of the stable replenisher was three times the capacity of the color developing tank.

As for the processing ratio of color paper and color negative film, running processing was performed at the area ratio of color paper 1 to color negative film 7.

After the running treatment was completed, the state of scum generation in the first stability tank was observed. Further, after the running process was completed, the magenta density of the unexposed area of the processed color paper sample was measured.

The results are summarized in Table 1.

Margin below In the above table, O means no scum has occurred, Δ means slight occurrence is observed, × means clear occurrence of scum, and roughly speaking, the greater the number of ×, the more scum has occurred. This means that there is a significant

From Table 1 above, 21! which satisfies the conditions of the present invention! When processing a combination of photosensitive materials, formalin-containing stabilizers and stabilizers without additives cause large scum and staining in the unexposed areas of the paper, but a stabilizer containing the compound of the present invention is used. By doing so, there will be no scum,
It can be seen that there are no density irregularities in the unexposed areas of the color paper.

Example 2 Compound A-1-1 of the present invention in the stabilizing solution used in Example 1
The concentration of
Running processing was performed in the same manner. At that time, the transmitted green density of the color negative film near the density 1.0 and the transmitted blue density of the unexposed area were measured, and
It was stored at 0% RH for 3 weeks, and the difference in concentration before and after storage was determined. Furthermore, the occurrence of scum in the first stability tank was also observed.

The results are summarized in Table 2.

Example 3 Using the color paper and color negative samples of Example 1, each coated silver amount was 0.58 g and 4.5 g per lrn', formaldehyde in the stabilizing solution was changed to the compound shown in Table 2, and the Example process was carried out. The same process was performed. After processing, the same evaluation as in Example 1 was carried out, and the color negative film sample and color paper sample were subjected to 3 cycles at 60°C and 80% RH.
The film was stored for a week, and the transmission green (G) density of the color negative film near the density 1.0 and the reflection red (R) density of the color paper at the highest density were measured before and after storage.

The results are summarized in Table 2 above.

From the results shown in Table 2 below, when color paper and color negative film are processed using the stabilizer containing the compound of the present invention, there is no scum generation in the stabilizer and no magenta tint on color paper, and color negative film and color It can be seen that there is little variation in density after storage of the paper.

Also F-1-10, F-3-1, F-3-4, F-4-1
, F-8-1, F-7-1, F-7-15, F-10-
13 and F-10-17 were also investigated, but almost the same effects as the exemplified compounds of the present invention could be obtained.

Example 4 The same experiment as in Example 1 was conducted by changing the silver halide composition of the color paper used in Example 3 in all layers (emulsion layer) as shown in Table 3. I investigated magenta tin.

As shown in Table 3, it can be seen that when samples with a molar ratio of silver chloride of 50 mol % or more are used, no scum is generated and there is no magentastin in the color pH unexposed areas.

Example 5 Using the color paper and color negative film samples used in Example 2, using exemplified compound A-1-1 in place of formaldehyde in the stabilizing solution, and changing the additive amount as shown in Table 4, Example 1 A similar experiment was conducted. The processed color paper and color negative film were stored under the conditions of Example 2, and the concentration fluctuations before and after storage were investigated. 0.05 to 10g per sentence is preferred.

Example 6 The cyan coupler in the color vapor sample used in the experiment of Example 1 was converted to
Cyan coupler (C'-2), (C'
-27), (C'-32), (C'-33), (C'-
34), (C'-38), (C'-37), (C'-3
8), (C'-39), (C'-53), (C''-2)
, (C″-8) and (C′-9), respectively,
When similar experiments were conducted, the reduction in red density was further improved by about 10 to 20%.

Example 7 The magenta coupler (M-2) in the color negative film sample prepared in Example 1 was replaced with the magenta coupler represented by the general formula (M-1), specifically the exemplified magenta coupler, 1, 2, 4. , 10°20, 21.3+, 40.8
The same experiment as in Example 1 was carried out except that the numbers were changed to 0.83.64, 74.78 and 81, respectively. As a result, the decrease in green density after storage of color negative film was 5 to 1.
0% improved. Scum has also been slightly improved overall.

Example 8 When the same experiment as in Example 1 was changed to the following treatment steps and the same treatment as in Example 1 was performed, the same results as in Example 1 were obtained. However, the same color developer and stabilizer as in Example 1 were used.

(The replenishment amount is the value per rn' of photosensitive material) Below margins Color negative film processing conditions The replenishment amount is the amount per rn' of photosensitive material.

Stabilization was carried out in a countercurrent manner from stability tank 3 to 1, and a portion of the stabilizing solution was flowed into the bleach-fixing solution (50 m/m').

The composition of each treatment liquid is as follows.

7 (tank fluid and refill fluid are the same) Ammonium thiosulfate (70%) 250ml
Ammonium thiocyanate 100g Sodium sulfite 20g Disodium ethylenediaminetetraacetate 5g Ammonium bromide
Add 40 g of water to make one sentence, and adjust to p)l 7.0 with acetic acid or ammonia wood.

Example 9 The same evaluation as in Example 1 was conducted, except that the stabilizer for color paper in Example 1 was changed to the composition shown below, and the treatment process was changed as shown in Figure 2. Almost the same effect was obtained, but the G density in the unexposed area of the color paper was improved by 0.01 to 0.02, and the scum generation in the first stabilizer tank also tended to improve. .

In FIG. 2, A indicates a processing step for color negative film, B indicates a processing step for color paper, and 10-a,
11-a, 12-a, 13-a, 14-a, and 15-a are color developing tanks, bleaching tanks, and bleaching tanks for color negative film processing, respectively;
Fixer tank, stable 4'l! IK! Eye, stabilization tank 2, stabilization tank 3 #1! 10-b, 11-b, +2-
b, +3-b, +4-b, and 15-b are a color developing tank, a bleaching tank, a fixing tank, a first stabilizing tank, a second stabilizing tank, and a third stabilizing tank for color paper processing.

The composition of the stabilizer and stable replenisher for color paper is as follows.

1.2 Pentzinthiazoline 3one O, 1g formaldehyde (37$W/W) or compound of the present invention See Table 1 Fluorescent brightener (Tinopar 5FP) 2. OgPH was adjusted to 8.5 and water was added to make one sentence.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram showing processing steps of an automatic developing machine used in an embodiment of the present invention, and FIG. 2 is an explanatory diagram showing other processing steps of the same automatic developing machine.

Claims (2)

[Claims] (1) The total coating amount of silver halide contained in the silver halide color photographic light-sensitive material is 2 g/m^2 to 10 g/m
A silver halide color photographic material (A) which is ^2,
At least two different types of silver halide color photographic light-sensitive materials (B) in which the total coating amount of silver halide contained in the silver halide color photographic light-sensitive material is 1 g/m^2 or less are mixed with hexamethylene. A silver halide color photographic light-sensitive material processed with a stabilizing solution containing a tetramine compound and at least one compound selected from the group of compounds represented by the following general formulas [F-1] to [F-10]. processing method. 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_1 to R_7_5 each represent a hydrogen atom or a methylol group. Furthermore, X represents an oxygen atom or a sulfur atom. ] 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 are a hydrogen atom and a lower alkyl group, respectively. or represents an electron-withdrawing group, and V_1 and W
They may be bonded at _1 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 represents a nitrogen atom and a group of nonmetallic atoms necessary to form a monocyclic or condensed nitrogen-containing heterocycle with the ▲numerical formula, chemical formula, table, etc. 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 at the same time. R_1_1 represents a hydrogen atom, a hydroxy group, an aliphatic group, or an aryl group. ] General formula [F-8] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula [F-9] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula [F-10] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [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 from 1 to 10, and Z_3 and R_1_3 each represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or Represents a group that is eliminated by hydrolysis. Z_3 may combine with R_1_3 to form a ring. ] (2) At least 50 mol% of the silver halide grains contained in the silver halide emulsion layer of the silver halide color photographic light-sensitive material (B) are silver chloride. Processing method for silver color photographic materials.