JPH05273718A - Processing method and processing liquid for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent decoloration of dye stuff and yellow stain when a picture is stored at low temp. and to improve storing property of liquid without incorporating formaldehyde in a stabilizer by incorporating a specified compd. into the stabilizer. CONSTITUTION:A silver halide color photographic sensitive material having at least one photosensitive silver halide emulsion layer on a supporting body is processed for monochromatic development and color development, and then processed with at least a stabilizer to form a color reversal image. In this process, a compd. expressed by formula I is incorporated into the stabilizer. In formula I, Z is atoms necessary to form a carbon ring or hetero ring, X is an aldehyde group or groups of formulae II, III, and n is an integer 1-4. In formulae II, III, R1 and R3 are lower alkyl groups. In the compd. expressed by formula I, it is preferable that the substituent for Z is an aldehyde group, hydroxyl group, alkyl group, etc., and more preferably, the photosensitive material contains a vinylsulfonic acid-base-hardening agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material and a processing solution used therefor,
More specifically, it relates to a method of processing a silver halide color photographic light-sensitive material having excellent stability of a dye image, improved scratch resistance, improved yellow stain, and excellent solution storability, and a processing solution used therefor.

[0002]

BACKGROUND OF THE INVENTION When processing a color photographic light-sensitive material for projection such as a color negative film or a color reversal film typified by a photographic light-sensitive material in which silver halide is silver iodobromide, a final processing step following a washing bath is conventionally used. Treatment baths containing formaldehyde are commonly used.

Formaldehyde used in the above treatment bath prevents physical properties of the color photographic light-sensitive material, especially scratches on the surface of the color photographic light-sensitive material and changes in gradation due to gradual hardening of the photographic light-sensitive material over time. It is known that there is an effect of improving the stability of the dye image due to the unreacted coupler remaining in the color photographic light-sensitive material.

However, formaldehyde, which is added to the processing bath for the purpose of stabilizing the dye image, adheres to the light-sensitive material and forms an adduct with sulfite ion brought in from the previous bath (processing solution having fixing ability). However, not only the effect of stabilizing the dye image, which is the original purpose, is reduced, but there is also a drawback that the sulfurization is promoted.

In particular, in the case of a color reversal film which undergoes bleaching and fixing treatments after black-and-white development and color development, and further is treated in a stabilizing bath, there is a high demand for stabilization of the dye image, and it is brought in from the pre-bath (treatment liquid having fixing ability). It is easily affected by the deterioration of the dye image stabilizing effect due to the reaction between sulfite ion and formaldehyde. Alternatively, the color reversal film has almost no mask density, and the effect of yellow stain on the unexposed portion is easily detected. Therefore, it is necessary to suppress the adverse effect of yellow stain that occurs after image storage as much as possible. In addition, the color reversal film remarkably suffers from adhesion to the light-sensitive material or occurrence of scratches due to sulfurization of the stabilizing solution.

To solve these problems, US Pat. No. 4,78
Although it has been proposed to use an alkanolamine as shown in Japanese Patent No. 6,583, the use of the alkanolamine tends to have an adverse effect on the yellow stain in the unexposed area, and it can be said that the sulfuration preventing effect is sufficient. It wasn't something.

On the other hand, formaldehyde is a CI in the United States.
Formaldehyde 1 by IT (Chemical Industry Association of Japan)
It was announced that nasal cancer occurred in rats at 5 ppm, and NIOSH (National Institute of Occupational Safety and Health), A
CGIH (Industrial Hygiene Government Specialist Council) also said that cancer may occur. Formaldehyde is also strongly regulated in Europe. In West Germany, formaldehyde was 0.1pp in homes from 10 years ago.
It is regulated to be less than m.

Further, in Japan, as harmfulness of formaldehyde, due to its stimulating action on mucous membranes, deleterious substances, deleterious drug laws, organic solvent poisoning regulation of labor safety law or household articles regulation, regulation on fiber and plywood And Showa 50
Since the year, the Ministry of Health and Welfare has begun to implement formaldehyde regulations on underwear and baby clothes, and a technology that can reduce formaldehyde has been long awaited.

As a technique for reducing the formaldehyde content in the stabilizing solution to substantially 0 or less, Japanese Patent Laid-Open No. 62-
The hexahydrotriazine compounds described in JP-A 27742 and JP 61-151538 A, and the N-methylol compounds described in U.S. Pat. No. 4,859,574 are disclosed as means for achieving the above object. ing.

However, although the hexahydrotriazine compound can prevent the dye from deteriorating under high temperature and high humidity even when the formaldehyde content becomes substantially 0, under low humidity, for example, when the relative humidity is 20% or less. Has a problem that it is not very effective, and there is a problem that the storage stability of the stabilizing solution is not so high as that of formaldehyde, especially that it is easily sulfurized.
It has been found that the storage stability becomes a problem particularly when the amount of treatment is low and when the amount of replenishment is low.

Further, the N-methylol compound, when used as a formaldehyde substitute compound, is not sufficient in terms of the dye fading prevention effect, backside stain and storability of the stabilizing solution. However, there is a problem that the storage stability of the solution is greatly deteriorated.

Further, as disclosed in US Pat. No. 4,960,682, it is disclosed that the preparation liquid contains the above N-methylol compound as a means for achieving the above object. However, even if the N-methylol compound is contained in the adjusting liquid, the fading of the dye can be prevented under high temperature and high humidity, but it is not so effective under low humidity, for example, when the relative humidity is 20% or less. However, there is a problem in that scum easily occurs due to a decomposed product of the N-methylol compound.

Further, a method of using a hexamethylenetetramine type compound in a stabilizing solution and other treating solutions has been disclosed, but it has a drawback that the effect of preventing dye fading under low humidity is weak like the hexahydrotriazine type compound.

As a result of studying various compounds in place of formaldehyde, the present inventors have found that a specific aromatic aldehyde is suitable, and include this in a fixing solution, an adjusting solution or a preliminary washing solution. Thus, the present invention has been reached, but the use of an aromatic aldehyde in a photographic processing liquid has been conventionally known. For example, JP-A-49-83441 and French Patent 1, The salicylaldehyde, furfural, 1-hydroxy-benzene-2,4-dialdehyde, etc. described in the specification of 543, 694 etc. were used.

However, these compounds are insufficient in the effect of the present invention, and as a result of investigations by the present inventors, surprisingly, by introducing a specific group at the meta position of benzaldehyde, a dye under a low humidity condition was surprisingly obtained. It has been found that it exhibits a sufficient effect on prevention of discoloration of, and yellow stain,
The present invention has been accomplished. However, as described above, the conventionally known aromatic aldehyde has a substituent group according to the present invention at the ortho position or the para position, and the effects of the present invention cannot be sufficiently obtained.

It is completely unthinkable to introduce such an effect by introducing a specific substituent at the meta position as described above, and the use of the compound according to the present invention provides another effect. It was also found that the scratch resistance was improved, and the present invention was achieved.

[0017]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is, firstly, to prevent fading of the dye under low humidity, secondly to improve the scratch resistance of the light-sensitive material, and thirdly to have excellent liquid storage stability, particularly sulfurization and scum. A processing method for silver halide color photographic light-sensitive material and a processing solution used therefor which can supply a processing solution which is less likely to cause, fourth, can improve yellow stain of unexposed area, and fifth can improve safety of working environment. Especially.

[0018]

DETAILED DESCRIPTION OF THE INVENTION We have at least one support on a support.
Method for processing a silver halide color photographic light-sensitive material, in which a silver halide photographic light-sensitive material having a light-sensitive silver halide emulsion layer is subjected to black-and-white development and color development, and then processed with at least a stabilizing solution to form a color reversal image. In the method of processing a silver halide color photographic light-sensitive material, the stabilizing solution contains a compound represented by the following general formula [F].

[0019]

[Chemical 5]

In the formula, Z represents an atomic group necessary for forming a carbocycle (including a substituent) or a heterocycle (including a substituent), X represents an aldehyde group,

[0021]

[Chemical 6]

(In these groups, R ₁ and R ₂ each represent a lower alkyl group), and n represents an integer of 1 to 4.

The above object of the present invention is achieved by the fact that the silver halide color photographic light-sensitive material contains a vinyl sulfonic acid type hardener.

Further, the above object of the present invention is to use a fixing solution or an adjusting solution or a preliminary washing solution for a silver halide color photographic light-sensitive material characterized by containing a compound represented by the following general formula [F]. Is achieved by

[0025]

[Chemical 7]

In the formula, Z represents an atomic group necessary for forming a carbocycle or a heterocycle, X represents an aldehyde group,

[0027]

[Chemical 8]

(In these groups, R ₁ and R ₂ each represent a lower alkyl group), and n represents an integer of 1 to 4. Still further, the object of the present invention is to process a silver halide color photographic light-sensitive material with a fixing solution or an adjusting solution or a preliminary washing solution for the silver halide color photographic light-sensitive material described above. This is achieved by the processing method of the photographic light-sensitive material.

The present invention will be described in detail below. In a preferred embodiment of the compound represented by the general formula [F], the substituent of Z is an aldehyde group, a hydroxyl group, an alkyl group, an aralkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfo group, a carboxy group, an amino group. Group, hydroxyalkyl group, aryl group, cyano group, aryloxy group, acyloxy group, acylamino group, sulfonamide group, sulfamoyl group, carbamoyl group or sulfonyl group.

In a further preferred embodiment, the silver halide color photographic light-sensitive material contains a vinyl sulfonic acid type hardener.

[Specific Structure of the Invention] The processing steps in the processing method using the color photographic processing liquid of the present invention include, but are not limited to, the following steps. (1) Color development → bleach-fixing → washing → stable (2) Color development → bleaching → fixing → washing → stable (3) Coloring development → bleaching → bleaching fixing → washing → stable (4) Coloring development → bleaching fixing → fixing → Washing → Stable (5) Color development → Bleach fixing → Bleach fixing → Water washing → Stable (6) Color development → Fixing → Bleach fixing → Water washing → Stable (7) Color development → Bleach → Bleach fixing → Fixing → Washing → Stable (8) ) Black and white development → Washing → Reversal → Color development → Washing → Adjustment →
Bleaching → Fixing → Washing → Stable (9) Black and white development → Washing → Inversion → Color development → Washing → Adjustment →
Bleach-fixing → Washing → Stable (10) Color development → Bleaching → Pre-washing → Fixing → Pre-washing →
Washing → Stable (11) Color development → Bleach → Fixing → Preliminary water washing → Stable (12) Color development → Bleach → Preliminary washing → Fixing → Washing → Stable (13) Color development → Bleach fixing → Stable (14) Color development → Bleaching → Fixing → Stable (15) Color development → Bleach → Bleach fixing → Stable (16) Color development → Bleach fixing → Fixing → Stable (17) Color developing → Bleach fixing → Bleach fixing → Stable (18) Color developing → Fix → Bleach Fixing → Stable (19) Color development → Bleach → Bleach fixing → Fixing → Stable (20) Black-white development → Wash → Reversal → Color development → Wash → Adjustment → Bleach → Fix → Stable (21) Black-white development → Wash → Reverse → Color development Development → washing → adjustment → bleach-fixing → stable (22) black-white development → washing → reverse → color development → adjustment → bleaching → fixing → washing → stable (23) black-white development → washing → reverse → color development → adjustment → bleach-fixing → Washing with water → Stable (24) Black and white development → In washing → reversal → color developing → Adjustment → bleach → fixing → stabilizing (25) black and white development → water washing → reversal → color developing → Adjustment → bleach-fixing → stabilizing present invention, a preferred treatment step (2), (4),
(8), (9), (10), (11), (12), (2
0) and (21), more preferably (2),
These are steps (8), (10), (11), (12), and (20). In the present invention, the preferred treatment step is
It is the step (1) or (3).

Next, the compound represented by the general formula [F] used in the present invention will be explained. In the general formula [F], Z represents an atomic group necessary for forming a carbocycle (including a substituent) or a heterocycle (including a substituent), and the carbocycle and the heterocycle may be monocycles. It may be a condensed ring, and Z is preferably an aromatic carbocycle or a heterocycle having a substituent.

The substituent of Z is an aldehyde group, a hydroxyl group,
Alkyl group (eg, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.), aralkyl group, alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.), halogen atom,
Nitro group, sulfo group, carboxy group, amino group (for example, N, N-dimethylamino, N-ethylamino, N-
Phenylamino etc.), hydroxyalkyl group, aryl group (eg phenyl, p-methoxyphenyl etc.), cyano group, aryloxy group (eg phenoxy, p-
Carboxyphenyl, etc.), acyloxy group, acylamino group, sulfonamide group, sulfamoyl group (eg,
N-ethylsulfamoyl, N, N-dimethylsulfamoyl, etc.), carbamoyl group (for example, carbamoyl,
N-methylcarbamoyl, N, N-tetramethylenecarbamoyl and the like), or a sulfonyl group (for example, methanesulfonyl, ethanesulfonyl, benzenesulfonyl, p-
It is preferably toluenesulfonyl or the like).

The carbocycle represented by Z is preferably a benzene ring, and the heterocycle represented by Z is preferably 5.
Is a 6-membered or 6-membered heterocycle, for example, a 5-membered ring is thiophene, pyrrole, furan, thiazole, imidazole, pyrazole, succinimide, triazole, tetrazole, etc., and a 6-membered ring is pyridine,
Pyrimidine, triazine, thiadiazine, etc. are respectively mentioned. As the condensed ring, naphthalene, benzofuran,
Examples thereof include indole, thionaphthalene, benzimidazole, benzotriazole, quinoline and the like. Preferred examples of the compound represented by formula [F] are shown below.

[0035]

[Chemical 9]

The exemplified compounds (F-1) to (F-52) can be obtained by inserting various substituents into 1 to 6 in the above formula as shown in the following table.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Chemical 10]

[0041]

[Chemical 11]

Specific examples of compounds other than these include compound examples (76) to (90) described on pages 13 to 14 of Japanese Patent Application No. 3-89686. Among the specific examples of the compounds represented by the general formula [F], more preferable compounds are (F-2), (F-3), (F-4),
(F-6), (F-23), (F-24), (F-5)
2) and (F-61) are mentioned, but (F-3) is most preferable.

The compound represented by the general formula [F] can be easily obtained as a commercial product. The compound represented by the general formula [F] is a treatment solution used in the pre-bath of a treatment bath having a bleaching ability together with a stabilizing solution, a treatment solution having a bleaching ability, a fixing solution or a preparation as long as the effect of the present invention is not impaired. It is contained in the liquid or the preliminary washing solution.

The addition amount of the compound represented by the general formula [F] is preferably 0.05 to 20 g, more preferably 0.1 to 15 g, and particularly preferably 0.3 to 10 g per liter of the treatment liquid. The range is.

The replenishing amount of the stabilizing solution is 6 per 1 m ² of the light-sensitive material.
It is 70 ml or less, preferably 100 ml or more and 500 ml or less, and more preferably 160 ml to 460 ml. If the supplement amount of the stabilizing solution exceeds 670 ml, the amount of the waste solution increases, which is not preferable in terms of social environment and economy, and the effect of the present invention is not remarkable.
The lower the replenishment is within the limit of milliliter / m ² , the more remarkable the effect of the present invention becomes.

In the present invention, the replenishment amount means a substantial replenishment amount, and when regenerating, the replenishment amount of the regenerant becomes the replenishment amount. In the present invention, the pH of the stabilizing solution is 6.0 or higher, preferably 7.0 or higher, more preferably 7.5.
~ 9.0. The pH adjusting agent that can be contained in the stabilizing solution may be any of commonly known alkaline agents or acid agents.

The component constituting the stabilizing solution used in the present invention is a compound represented by the general formula [F], preferably a surfactant, (general formula [I] or [II]).
And organic acid salts, pH adjusters, antifungal agents and the like. In the present invention, the effects of the present invention are more effectively exhibited when a vinyl sulfone type hardener is used in the light-sensitive material.

The vinyl sulfone type hardener used in the present invention is a compound having a vinyl group bonded to a sulfonyl group or a group capable of forming a vinyl group, and preferably,
It has at least two vinyl groups bonded to a sulfonyl group or groups capable of forming a vinyl group. For example, the compound represented by the following general formula [VS-1] is preferably used in the present invention.

General formula [VS-1] L- (SO ₂ -X) _{m In the} above general formula [VS-1], L is an m-valent linking group, and X is -CH = CH ₂ or -CH _2. CH ₂ Y, Y represents a group capable of being eliminated in the form of HY by a base, such as a halogen atom, a sulfonyloxy group, a sulfooxy group (including a salt), a residue of a tertiary amine, and the like. m is 2 to 1
Represents an integer of 0, in which case -SO ₂ -X is the same,
They may be different from each other.

The m-valent linking group L is, for example, an aliphatic hydrocarbon group (eg, alkylene, alkylidene, alkylidyne or the like or a group formed by combining these), an aromatic hydrocarbon group (eg, arylene or the like or these Formed by bonding with each other), -O-, -NR'- (R 'represents a hydrogen atom or preferably an alkyl group having 1 to 15 carbon atoms), -S-, -N <, -CO. -, - SO -, - SO 2
Or an m-valent group formed by combining one or more bonds represented by —SO ₃ —, and —N
When two or more R'- are included, these R's may be bonded to each other to form a ring.

The linking group L 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. Examples of X, -CH = CH ₂ or -CH ₂ CH ₂ Cl
Etc. are preferred.

Typical specific examples of the vinyl sulfone type hardener are shown below.

[0053]

[Chemical 12]

Other specific examples of compounds include (VS-1), (VS-3), (VS-5) and (VS) described on pages 122 to 128 of Japanese Patent Application No. 274040/1990.
-7), (VS-8), (VS-11), (VS-1)
3) to (VS-21), (VS-23) to (VS-3)
2), (VS-34) to (VS-53), (VS-5)
5) to (VS-57). Among the specific examples of these compounds, more preferable compounds include (VS-
6), (VS-9), (VS-10), (VS-1
2), (VS-22), (VS-33), (VS-5)
4).

The vinyl sulfone type hardener used in the present invention is, for example, an aromatic compound as described in German Patent 1,100,942 and US Pat. No. 3,490,911. 44-29622, 47-25
No. 373, No. 47-24259, etc., and an alkyl group compound bonded with a hetero atom, as described in JP-B No.
7-8736, a sulfonamide as described in 7-8736,
Ester compounds, 1,3,5-tris [β- (vinylsulfonyl) -propionyl] -hexahydro-s-triazine as described in JP-A-49-24435 or JP-B-50-35807, Kaisho 51-4
4164 and the like, and alkyl compounds such as those described in JP-A-59-18944 and the like.

These vinyl sulfone type hardeners are dissolved in water or an organic solvent, and 0.005 to 20% by weight, preferably 0.02 to 20% by weight, based on the binder (eg gelatin).
10% by weight is used. A batch method or an in-line addition method is adopted for addition to the photographic layer. The layer of addition of these hardeners to the photographic layer is not particularly limited,
For example, it may be added to the uppermost layer, the lowermost layer, or all layers. Further, 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].

[0057]

[Chemical 13]

In the formula, R ¹ represents an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, an amino group, a carboxylic acid group (including its salt) or a sulfonic acid group (including its salt). R ² and R ³ are each a hydrogen atom, a halogen atom, an amino group, a nitro group, a hydroxyl group,
It represents an alkoxycarbonyl group, a carboxylic acid group (including its salt) or a sulfonic acid group (including its salt). M represents a hydrogen atom, an alkali metal atom or an ammonium group.

[0059]

[Chemical 14]

In the formula, R ⁴ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogenated alkyl group, or -R ¹²
-OR ¹³ -CONHR ¹⁴ (wherein R ¹² represents an alkylene group, R ^13, R ¹⁴ each represent a hydrogen atom, an alkyl group or an arylalkyl group.) Or an arylalkyl group, R ⁵ and R ⁶ each Represents a hydrogen atom, a halogen atom, a halogenated alkyl group or an alkyl group, R ⁷
Is a hydrogen atom, a halogen atom, an alkyl group, an aryl group,
Halogenated alkyl group, an arylalkyl group, -R ¹⁵ -
Represents OR ¹⁶ or —CONHR ¹⁷ (wherein R ¹⁵ represents an alkylene group, R ¹⁶ and R ¹⁷ both represent a hydrogen atom or an alkyl group), and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ respectively. It represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an amino group or a nitro group.

Next, the compounds represented by the general formulas [B-1] to [B-3] will be described. Specific examples of the compound represented by the general formula [B-1] include the following exemplified compounds.

[0062]

[Chemical 15]

Specific examples of compounds other than these include:
Japanese Patent Application No. 2-274026, pages 130 to 132
(B-1-4) to (B-1-15) and (B-1)
-17) can be mentioned. Some of the compounds represented by the above general formula [B-1] are known as preservatives such as mandarin orange and are commercially available, and those skilled in the art can easily obtain them. General formula [B-1] used in the present invention
The compound can be contained in the stabilizing solution of the present invention, and is preferably used in an amount of 0.03 to 50 g, more preferably 0.12 to 10 g, and particularly preferably 0.15 to 1 g per liter of the stabilizing solution. It is 5 g. The general formula [B-
Specific examples of the compound represented by 2] and [B-3] will be described below, but the invention is not limited thereto.

(B-2-1) 2-Methyl-4-isothiazolin-3-one (B-2-2) 5-chloro-2-methyl-4-isothiazolin-3-one (B-2-3) 2-Methyl-5-phenyl-4-isothiazolin-3-one (B-2-4) 4-bromo-5-chloro-2-methyl-
4-isothiazolin-3-one (B-2-5) 2-hydroxymethyl-4-isothiazolin-3-one (B-2-6) 2- (2-ethoxyethyl) -4-isothiazolin-3-one (B-2-6) B-2-7) 2- (N-methyl-carbamoyl) -4
-Isothiazolin-3-one (B-2-8) 5-bromomethyl-2- (N-dichlorophenyl-carbamoyl) -4-isothiazolin-3-
On (B-2-9) 5-chloro-2- (2-phenylethyl) -4-isothiazolin-3-one (B-2-10) 4-methyl-2- (3,4-dichlorophenyl) -4 -Isothiazolin-3-one (B-3-1) 1,2-benzisothiazolin-3-one (B-3-2) 2- (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-Benzyl-1,2-benzisothiazolin-3-one (B-3-6) 5-chloro-1,2-benzisothiazolin-3-one

These exemplified compounds are described in US Pat.
No. 7,172, No. 2,767,173,
No. 2,767,174, No. 2,870,015
Nos. 5,848,130, French Patent 1,555,416 and the like describe synthetic methods and examples of application to other fields. There are also commercially available products such as Topside 300 (Permachem Asia Co., Ltd.), Topside 600 (Permachem Asia Co., Ltd.), Fineside J-700 (Tokyo Fine Chemical Co., Ltd.), Proxel GXL (I .CI
It is available under the trade name of (Ltd.).

The compounds represented by the general formulas [B-1] to [B-3] are 0.1 to 500 m / m ² of the light-sensitive material.
It is used in the range of g, preferably in the range of 0.5 to 100 mg. Further, these general formulas [B-1] to [B
-3] may be used in combination of two or more kinds. In the stabilizing solution, the following general formula [I] or [I
I] is included. General formula (I) _{R 3 -O- (R 4 -O)} m -X 1 Formula, R ₃ represents a monovalent organic group, R ₄ is an ethylene group,
Represents a trimethylene group or a propylene group, m is 4 to 50
Represents the integer. X ₁ is a hydrogen atom, -SO ₃ M or -PO
Represents ₃ M. Here, M represents a hydrogen atom, an alkali metal atom or an ammonium group.

[0067]

[Chemical 16]

In the formula, R ₅ is a hydrogen atom, a hydroxy group, a lower alkyl group, an alkoxy group,

[0069]

[Chemical 17]

Represents R ₆ , R ₇ and R ₈ are each a hydrogen atom or a lower alkyl group (preferably having 1 carbon atom).
To 4 alkyl groups such as a methyl group, an ethyl group and a propyl group. ), And R ₆ , R ₇ and R ₈ may be the same or different. k _{1 to} k ₃ each represent an integer of 0 or 1 to 4, and p, q ₁ and q ₂ each represent an integer of 0 or 1 to 15. X ₂ and X ₃ are ethylene group, trimethylene group, —CH ₂ CH (CH ₃ ) —
Or -CH (CH ₃₎ -CH ₂ - represents a.

Specific examples of compounds represented by the general formula [I] are shown below.

[0072]

[Chemical 18]

Other specific exemplified compounds include (I-2), (I-3), (I-4), ((I-2) described on page 63 to page 65 of Japanese Patent Application No. 274040/1990. I-7) ~
(I-11), (I-13), (I-15) to (I-1
9) can be mentioned. These compounds represented by the general formula [I] can be used in the stabilizing solution used in the present invention in an amount of 0.1 to 40 g per liter, preferably 0.3 to 20 g. ..

Next, specific examples of the compound (water-soluble organic siloxane compound) represented by the general formula [II] will be shown.

[0075]

[Chemical 19]

Other specific examples Exemplified compounds include (II-1), (II-2), (II-5) to (II-1) described on pages 67 to 70 of Japanese Patent Application No. 274040/1990. (II
-7), (II-9) to (II-11), (II-1)
3), (II-14) and (II-17).

The amount of the water-soluble organic siloxane compound having a polyoxyalkylene group added has a good effect when it is used in the range of 0.01 to 20 g per liter of the stabilizing solution, and particularly, precipitation prevention and yellow It is effective in preventing the occurrence of stains. If it is less than 0.01 g / liter, stains on the surface of the light-sensitive material are conspicuous, and if it exceeds 20 g / liter, a large amount of the organosiloxane compound adheres to the surface of the light-sensitive material, resulting in accelerated stain.

The water-soluble organic siloxane compound used in the present invention is disclosed, for example, in JP-A-47-18333, JP-B-55-51172, JP-B-51-37538 and JP-A-49-62128. And US Pat. No. 3,54
It means a general water-soluble organic siloxane-based compound as described in Japanese Patent No. 5,970. These water-soluble organosiloxane compounds can be generally obtained from UCC (Union Carbide Co., Ltd.) and Shin-Etsu Chemical Co., Ltd.

In the present invention, the stabilizing solution preferably contains a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the chelate stability constant is
L. G. Sillen A. E. By Martell, ”
Stability Constants of Me
tal-ion Complexes ”, The Ch
electronic Society, London (196
4), S. Chaberek A .; E. Martell
Written by "Organic Sequestering"
It means a constant generally known from Agents ”, Willey (1959) and the like.

The chelate stability constant for iron ions is 8
As the chelating agent as described above, an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent,
Examples thereof include polyhydroxy compounds. The iron ion means ferric ion (Fe ³⁺ ).

The chelate stability constant with ferric ion is 8
Specific examples of the above chelating agent include, but are not limited to, the following compounds. That is, ethylenediaminedioltohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, Diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,
Examples thereof include 3-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate and sodium hexametaphosphate, particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid,
Examples thereof include nitrilotrimethylenephosphonic acid and 1-hydroxyethylidene-1,1-diphosphonic acid, and among them, 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

The amount of the above chelating agent used is preferably 0.01 to 50 g, and more preferably 0.05 to 20 g per liter of the stabilizing solution, and good results are obtained. Further, as a preferable compound added to the stabilizing solution, an ammonium compound can be mentioned. These are supplied by ammonium salts of various inorganic compounds, and specifically, ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium phosphate and the like. These may be used alone or in combination of two or more. The addition amount of the ammonium compound is preferably in the range of 0.001 to 1.0 mol, and more preferably 0.002 to 2.
It is in the range of 0 mol.

The stabilizing solution preferably contains a metal salt in combination with the chelating agent. Examples of such metal salts include B
a, Ca, Ce, Co, In, La, Mn, Ni, B
i, Pb, Sn, Zn, Ti, Zr, Mg, Al or S
There are metal salts of r, halides, hydroxides, sulfates,
It can be supplied as an inorganic salt such as a carbonate, a phosphate or an acetate, or as a water-soluble chelating agent. The amount used is preferably in the range of 1 × 10 ^-4 to 1 × 10 ^-1 mol per liter of the stabilizing solution,
More preferably, it is in the range of 4 × 10 ⁻⁴ to 2 × 10 ⁻² mol.

The stabilizing solution contains organic acid salts (citric acid, acetic acid,
Succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphate, borate, hydrochloric acid, sulfate, etc.) and the like can be added. These compounds may be added in any combination so long as they are necessary for maintaining the pH of the stabilizing bath and do not adversely affect the stability during storage of color photographic images and the occurrence of precipitation. I don't care. In the present invention, known antifungal agents can be used alone or in combination as long as the effects of the present invention are not impaired.

In the process used in the present invention, silver may be recovered from the stabilizing solution. For example, electrolysis method (described in French Patent 2,299,667), precipitation method (described in JP-A-52-73037, German Patent 2,33).
No. 1,220), ion exchange method (JP-A-51)
-17114, German Patent 2,548,237
Specification) and metal substitution method (UK Patent 1,353,
No. 805 specification) can be effectively used. These silver recovery methods are particularly preferable when in-line silver recovery from a tank solution using an electrolysis method or an anion exchange resin further improves the suitability for rapid processing, but it is particularly preferable, but silver recovery from overflow waste solution may be carried out and recycled. ..

Further, the stabilizing solution is subjected to ion exchange treatment, electrodialysis treatment (see JP-A-61-28949) and reverse osmosis treatment (JP-A-60-240153 and JP-A-62-25415).
No. 1), etc. Further, it is also preferable to use deionized water used in the stabilizing solution in advance. That is, the antifungal property of the stabilizing solution, the stability of the stabilizing solution and the image storability are improved.

Any means can be used for the deionization treatment so long as the Ca and Mg ions in the wash water after the treatment are 5 ppm or less. For example, a treatment with an ion exchange resin or a reverse osmosis membrane is used alone or in combination. Preferably. Regarding the ion exchange resin and reverse osmosis membrane, open technical report 87
-1984 and Open Technical Report 89-20511 are described in detail. The salt concentration in the stabilizing solution is preferably 1000 ppm or less, more preferably 800 ppm or less.

No washing treatment is required after the stabilizing treatment, but rinsing by a small amount of washing in a very short time, surface washing and the like can be optionally performed.

Next, the fixing solution in the present invention will be described in detail. The fixing solution is a solution containing a silver halide fixing agent in the processing solution, and this fixing solution includes, for example, a fixing solution (including an acidic hardening fixing solution) and a bleach-fixing solution. Be done.

Specific examples of the thiocyanate and iodide (both may be collectively referred to as the compound of the present invention hereinafter) contained in the fixing solution of the present invention are shown below. Is not limited to these.

F-1 Ammonium thiocyanate F-2 Potassium thiocyanate F-3 Sodium thiocyanate F-4 Thiocyanocatechol F-5 Ammonium iodide F-6 Potassium iodide F-7 Sodium iodide F-8 Thiosulfate Sodium F-9 Ammonium thiosulfate F-10 Potassium thiosulfate

Among the compounds according to the present invention, preferred examples are (F-1), (F-2), (F-3) and (F-5),
(F-9), and more preferably (F-1), (F-
2) and (F-3). The compound according to the present invention may be used alone or in combination of two or more.

When the compound of the present invention is thiocyanate or thiosulfate, the compound of the present invention exhibits the effect of the present invention by containing at least 1.0 mol per liter of the processing solution having fixing ability. It is preferably 1.2 mol or more and 5.0 mol or less, more preferably 1.5 mol or more and 4.5 mol or less, and most preferably 2.0 l or more and 4.0 mol or less, per liter of the treatment liquid.

When the compound according to the present invention is an iodide ion, it is preferably 2 mol or more and 10 mol or less, more preferably 3 mol or more and 8 mol or less, per liter of the treatment liquid.
Particularly preferably, it is 4 l or more and 6 mol or less. In carrying out the present invention, silver may be recovered by a known method from a processing solution having a fixing solution, that is, a fixing solution or a bleach-fixing solution.

For example, electrolysis (French Patent 2,299,6
67), precipitation method (JP-A-52-73037, German Patent 2,331,220), ion exchange method (JP-A 51-17114, German Patent 2,54).
No. 8,237) and metal substitution method (UK Patent 1,35)
No. 3,805) can be effectively used. These silver recovery methods are particularly preferable because in-line silver recovery from the tank liquid further improves the suitability for rapid processing, but silver recovery from the overflow waste liquid may be carried out and recycled.

The fixing solution and the bleach-fixing solution of the present invention exhibit the effects of the present invention more favorably when the replenishing amount is 800 ml or less per 1 m ^{2 of the} light-sensitive material. Particularly good results are obtained with 20 to 650 ml, and particularly 30 to 400 ml per 1 m ^{2 of the} light-sensitive material.

When the fixing solution or the bleach-fixing solution according to the present invention is used by adding the compound represented by the following general formula [FB], not only the effects of the present invention are more favorably exhibited but also cyan It is more preferably used in the present invention because it has the additional effect of improving the color recovery of the dye.

Next, the compound represented by the general formula [FB] will be described in detail.

[0099]

[Chemical 20]

In the general formula [FB], R ₁ , R ₂ , R
₃ and R ₄ each represent a hydrogen atom, an aliphatic group, an aryl group, an acyl group or an amino group. R ₁ and R ₃ , and R ₂ and R ₄ may be connected to each other to form a ring. Further, R ₁ and R ₂ , and R ₃ and R ₄ may be connected to each other to form a ring.

The aliphatic group represented by R _{1 to} R ₄ is an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), a substituted alkyl group (for a substituent, for example, a hydroxy group, a carboxylic acid group, Examples thereof include a mercapto group, a sulfonamide group, an alkylamino group, an amino group and a sulfonic acid group), an alkenyl group (eg allyl group) and a cycloalkyl group (eg cyclohexyl group).

The aryl group represented by R _{1 to} R ₄ is, for example, a phenyl group, a substituted phenyl group (eg, a substituent is a halogen group (chloro group, bromo group, etc.), an alkyl group (methyl group, ethyl group, etc.). Etc.) and the like. Examples of the acyl group represented by R _{1 to} R ₄ include an acetyl group.

Examples of the amino group represented by R _{1 to} R ₄ include an unsubstituted amino group and a substituted amino group (as the substituent, an aryl group such as a phenyl group, an alkyl group such as a methyl group and an ethyl group, and a thioamide group). be able to. In addition, examples of forming each of the above rings include a 5-membered ring and a 6-membered ring, and may be a saturated ring or an unsaturated ring. R ₁
And R ₂ and R ₃ and R ₄ are combined with each other to form a nitrogen-containing heterocycle (eg, morpholino, piperazino, piperidino, pyrrolidine, etc.).

Specific examples of the compounds represented by formula [FB] are shown below.

[0105]

[Chemical 21]

[0106]

[Chemical formula 22]

[0107]

[Chemical formula 23]

[0108]

[Chemical formula 24]

The thiourea represented by the general formula [FB] and its derivatives can be synthesized by the conventionally known Rodan Ammon method, diazomethane method, lime nitrogen method, etc., and some of them are commercially available as chemical products. There is. Alternatively, JP-A-63-22
It can be synthesized by a general method as described in 9449, U.S. Pat. No. 3,801,330 and British Patent 931,560.

The amount of the compound represented by the above-mentioned general formula [FB] added to the processing solution having fixing ability is not less than 0.1 g / liter and the maximum dissolving amount of each compound is preferable, but is preferably 0.3. It is used in the range of 50 to 50 g / liter, and more preferably in the range of 0.5 to 25 g / liter.

The processing solutions having fixing ability of the present invention include sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite and sodium metabisulfite. P consisting of salts and various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide
The H buffer may be used alone or in combination of two or more.

Further, it is desirable to add a rehalogenating agent such as an alkali halide or an ammonium halide such as potassium bromide, sodium bromide, sodium chloride or ammonium bromide in an amount. In addition, buffers such as borate, oxalate, acetate, carbonate, phosphate, phosphate, and the like, which are known to be added to ordinary fixing solutions and bleach-fixing solutions of alkylamines and polyethylene oxides are appropriately used. It can be added.

Further, the addition amount of the compound represented by the general formula [FA] and the compound represented by the general formula [FB] is preferably in the range of 0.1 to 200 g per liter of the treatment liquid. Especially, the range of 0.2 to 50 g is preferable,
The range of 0.5 to 10 g is particularly preferable. A sulfurous acid adduct is preferably used in the fixing solution and the bleach-fixing solution of the present invention from the viewpoint of the effects of the present invention.

Examples of the compound capable of forming a stable sulfite adduct with sulfite ion include a compound having an aldehyde group, a compound having a cyclic hemiacetal, a compound having an α-dicarbonyl group and a nitrile group. Examples of the compound include compounds, and the compound represented by the following general formula [AI] or [A-II] is particularly preferably used.

[0115]

[Chemical 25]

A ₂ , A ₃ , A ₄ and A ₅ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group or an alkenyl group. The alkyl group having 1 to 6 carbon atoms includes straight-chain or branched ones, for example, a methyl group,
Ethyl group, n-propyl group, iso-propyl group, n-
Examples thereof include a butyl group, an n-barrel group, an iso-barrel group, a hexyl group, and an isohexyl group, which may be substituted. Specifically, a formyl group (eg, formylmethyl,
2-formylethyl etc.), amino group (eg aminomethyl, aminoethyl etc.), hydroxyl group (eg hydroxymethyl, 2-hydroxyethyl, 2
-Hydroxypropyl etc.), alkoxy groups (e.g. methoxy, ethoxy, etc.), halogen atoms (e.g., chloromethyl, trichloromethyl, dibromomethyl, etc.), and other substituents.

The alkenyl group includes substituted and unsubstituted groups, the unsubstituted group includes groups such as vinyl and 2-propenyl, and the substituted groups include, for example, 1,2-
Examples thereof include groups such as dichloro-2-carboxyvinyl and 2-phenylvinyl. Hereinafter, specific examples of the compound that forms a stable sulfite adduct with the sulfite ion will be described.

[0118]

[Chemical formula 26]

AO-11 Sodium formaldehyde bisulfite AO-12 Sodium acetaldehyde bisulfite AO-13 Sodium propionaldehyde bisulfite AO-14 Sodium butyraldehyde bisulfite AO-21 Sodium succinate bisulfite AO-22 Glutaraldehyde bisbisulfite Sodium AO-23 β-methyl aldehyde bis sodium bisulfite AO-24 Maleic acid dialdehyde bis sodium bisulfite

These sulfurous acid addition compounds are preferably used in an amount of 0.1 to 80 g, and more preferably 0.5 to 40 g, per liter of the treatment liquid. The fixing solution of the present invention preferably has a treatment time of 3 minutes or less, more preferably 20 seconds to 2 minutes or less, and particularly preferably 30 seconds to 2 minutes to obtain the desired effects of the present invention. To play.

The silver may be recovered from the fixing solution or the bleach-fixing solution by a known method. The amount of replenishment of the fixing solution is 1
Usually, 50 ml to 900 ml per m ² is used, preferably 100 ml to 500 ml. The pH of the fixing solution is preferably in the range of 4-8.

Next, the adjusting liquid in the present invention will be described in detail. After the color development process, the adjusting solution is a process for washing out and detoxifying the sensitizing dyes, dyes and other sensitive material parts contained in the photographic light-sensitive material and the color-developing agent impregnated in the photographic light-sensitive material. That liquid.

The above-mentioned preparation liquid contains aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-propanediaminetetraacetic acid and cyclohexanediaminetetraacetic acid, sulfite salts such as sodium sulfite and ammonium sulfite, Also, various bleaching accelerators such as thioglycerin, aminoethanethiol, and sulfoethanethiol described in the bleaching solution can be contained. Also, for the purpose of preventing scum, US Pat.
Sorbitan esters of fatty acids substituted with ethylene oxide as described in US Pat. No. 9,262, US Pat.
No. 46 and Research Disclosure 191, 1
It is preferable to include the polyoxyethylene compound described in 9104 (1980).

Preliminary water washing in the present invention means washing the bleaching agent impregnated in the photographic light-sensitive material after bleaching to render it harmless, and washing the fixing agent impregnated in the photographic light-sensitive material after fixing treatment and harmless. May be converted. The prewash solution used in the present invention preferably contains a mildew proofing agent, which can further improve sulfuration prevention and image storability.

Examples of the antifungal agent include isothiazoline type, benzimidazole type, benzisothiazoline type,
Siabendazole-based compounds, phenol-based compounds, organic halogen-substituted compounds, mercapto-based compounds, benzoic acid and its derivatives can be used, but preferably isothiazoline-based, benzisothiazoline-based, siabendazole-based,
Phenolic compounds, benzoic acid and the like can be mentioned. Particularly preferred are isothiazoline-based and siabendazole-based compounds. Specific compounds will be listed below, but the invention is not limited thereto.

[Exemplified Compound] (1) 2-Methyl-4-isothiazolin-3-one (2) 5-Chloro-2-methyl-4-isothiazolin-3-one (3) 2-Methyl-5-phenyl- 4-Isothiazolin-3-one (4) 4-Bromo-5-chloro-2-methyl-4-isothiazolin-3-one (5) 2-Hydroxymethyl-4-isothiazolin-
3-one (6) 2- (2-ethoxyethyl) -4-isothiazolin-3-one (7) 2-(-methyl-carbamoyl) -4-isothiazolin-3-one (8) 5-bromomethyl-2- (N-Dichlorophenyl-carbamoyl) -4-isothiazolin-3-one (9) 5-chloro-2- (2-phenylethyl) -4
-Isothiazolin-3-one (10) 4-methyl-2- (3,4-dichlorophenyl) -4-isothiazolin-3-one (11) 1,2-benzisothiazolin-3-one (12) 2- (2 -Bromoethyl) -1,2-benzisothiazolin-3-one (13) 2-methyl-1,2-benzisothiazolin-
3-one (14) 2-ethyl-5-nitro-1,2-benzisothiazolin-3-one (15) 2-benzyl-1,2-benzisothiazolin-3-one (16) 5-chloro-1, 2-benzisothiazoline-
3-one (17) Hydroxybenzoic acid (18) Siabendazole

For these exemplified compounds, US Pat. Nos. 2,767,172, 2,767,173, 2,767,174, 2,870,015, British Patent 848,130, and US Pat. French Patent 1,555,4
No. 16, etc., describes its synthesis method and application examples to other fields. There are also commercially available products such as Topside 300, Topside 600 (all manufactured by Permachem Asia Co., Ltd.), Fineside J-700 (manufactured by Tokyo Fine Chemical Co., Ltd.), Proxel GXL (manufactured by ICI).
It is available under the brand name of.

The amount of the above-mentioned compound used is preferably 0.01 to 50 g, and more preferably 0.05 to 20 g, per liter of the preliminary washing solution. Further, as other compounds that can be added to the preliminary washing solution in the present invention,
Organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH buffers (phosphoric acid, borate, hydrochloric acid, sulfuric acid, etc.) or surfactants, preservatives, Bi, Mg, Zu,
There are metal salts such as Ni, Al, Sn, Ti, Zr, etc.,
The amount of these compounds added is within the range required to maintain the pH of the stabilizing solution according to the present invention and does not adversely affect the stability during storage of color photographic images and the occurrence of precipitation. It does not matter even if it is used in such a combination.

The treatment temperature for the stabilizing treatment is 50 ° C. or lower, preferably 15 ° C. to 50 ° C., more preferably 2 ° C.
The range of 0 ° C to 45 ° C is preferable. The processing time is preferably as short as possible from the viewpoint of rapid processing, but it is usually 20 seconds to 1
It is 0 minutes, most preferably 1 minute to 5 minutes, and in the case of the multi-tank stabilization treatment, it is preferable that the treatment is performed in a shorter time in the former tank and longer in the latter tank. Especially 20% of the previous tank
It is desirable to perform the treatment sequentially with the treatment time increased by 50%.
(While no washing treatment is required before and after the stabilization treatment according to the present invention, a rinse with a small amount of washing in an extremely short time,
Surface cleaning and the like can be optionally performed as needed. )

When the multi-tank counter current system is used as the method for supplying the pre-rinsing solution in the pre-rinsing treatment step according to the present invention, it is preferable that the pre-rinsing solution is supplied to the post-bath and overflows from the pre-bath. Of course, it can also be processed in a single tank.
When the amount of replenishment is 2500 ml or less per 1 m ² of the light-sensitive material, the effect of the present invention is better exhibited. Particularly good results are obtained with 20 to 2000 ml, and particularly 30 to 1500 ml per 1 m ^{2 of the} light-sensitive material.

The black-and-white developing agent used in the present invention is described in, for example, T. James, "The Photographic Process (1977)" T.W. H. James "
The Theory of the Photogr
The compounds described on pages 300 to 327 of "Apic Process (1977)" can be used,
Specifically, hydroquinones such as hydroquinone,
2,3-dimethylhydroquinone and the like, and para-aminophenols such as para-aminophenol and N-methyl-para-aminophenol.

Further para-aminophenols include 1-phenyl-3-pyrazolidones such as 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone,
It is preferable that 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone or the like is used in combination. Other developing agents known in the photographic industry can be used. Further, various components usually added such as an alkali preservative, a development accelerator, an antifoggant, a chelating agent, and a thickening agent can be added to the black and white developer.

The color developing agent used in the color developing solution in the present invention is preferably an aromatic primary amine color developing agent, and includes various kinds widely used in various color photographic processes. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example hydrochlorides or sulphates.

As the color developing agent used in the color developing treatment step, there are aminophenol compounds and p-phenylenediamine compounds, and the effective color developing agent used in the present invention is at least 1 on the amino group.
Para-phenylenediamine color developing agents having two water-soluble groups (hydrophilic groups). Typical examples of these color developing agents include the following compounds, but the present invention is not limited thereto. is not. Such a water-soluble group has at least one on the amino group or the benzene nucleus of the p-phenylenediamine compound, and as a specific water-soluble group,

-(CH ₂ ) _n --CH ₂ OH,-(C
_{H 2) m -NHSO 2 - (} CH 2) n -CH 3, - (C
_{H 2) m -O- (CH 2} ) n -CH 3, - (CH 2 CH
₂ O) _n C _m H _{2 m + 1} (m and n each represent an integer of 0 or more), —COOH group, —SO ₃ H group and the like can be mentioned as preferable ones.

[0136]

The color developing solution may contain a known developing component in addition to the aromatic primary amine color developing agent. For example, preservatives, alkali agents, buffers, antifoggants, development inhibitors, and if necessary development accelerators, organic solvents, chelating agents and the like. Further, an auxiliary developing agent can be used together with the developing agent. In addition, if necessary, a competing coupler, a fogging agent, a colored coupler, a development-inhibiting release type coupler, a development-inhibiting agent-releasing compound or the like may be added.

Specific examples of the color developing agent preferably used in the present invention include (A-1) to (A-) described on pages 80 to 83 of Japanese Patent Application No. 274040/1990.
16).

The amount of the color developing agent added is preferably 0.5 × 10 ^-2 mol or more, and more preferably 1.0 × 10 ^{-2 to} 1.0 × 1 per liter of the color developing solution.
It is in the range of 0 ⁻¹ mol, most preferably 1.5 × 10 ⁻²
It is in the range of -10 ^-2 mol. The color developing agent is usually used in the form of a salt such as a hydrochloride, a sulfate or a p-toluenesulfonate.

The color developing solution used in the color developing processing step is an alkali agent usually used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or the like. Borax and the like can be included.

Further, various additives such as benzyl alcohol, alkali halides such as potassium bromide or potassium chloride, or development regulators such as citrazinic acid, and preservatives such as hydroxylamine and hydroxylamine derivatives (eg, diethyl ether). Hydroxylamine), a hydrazine derivative (eg, hydrazinodiacetic acid), a sulfite salt, or the like.

Furthermore, various antifoaming agents and surfactants are added.
Further, an organic solvent such as methanol, dimethylformamide or dimethylsulfoxide may be appropriately contained. The pH of the color developer is usually 7 or higher, preferably about 9-13. In the color developing solution, tetronic acid, tetronimide, 2-
Anilinoethanol, dihydroxyacetone, secondary aromatic alcohol, hydroxamic acid, bentose or hexose, pyrogallol-1,3-dimethyl ether and the like may be contained.

Various chelating agents can be used in combination in the color developer as a sequestering agent. For example, as the chelating agent, an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-
Organic phosphonic acids such as hydroxyethylidene-1,1-diphosphonic acid, aminopolyphosphonic acids such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1,2. , 4-tricarboxylic acid and other phosphonocarboxylic acids, tripolyphosphoric acid, hexametaphosphoric acid and other polyphosphoric acids, and the like.

The replenishing amount of the color developing solution in the continuous processing is preferably 1.5 liters or less per 1.0 m ² of the light-sensitive material for the color negative film, more preferably 100 to 900 ml, and further preferably 200 to 700. It is milliliter.

The bleaching agent used in the processing solution, that is, the stabilizing solution or the bleaching solution or the bleach-fixing solution in the present invention is a ferric complex salt of an organic acid represented by the following general formula [A] and the following (A ').
-1) to (A'-16) and the second of the exemplified compounds represented by
An iron complex salt is mentioned.

[0146]

[Chemical 28]

In the general formula [A], A _{1 to} A ₄ may be the same or different and each is --CH ₂ OH or --C.
Represents OOM or —PO ₃ M ₁ M ₂ , M, M ₁ and M ₂
Each represents a hydrogen atom, an alkali metal atom (eg sodium, potassium) or an ammonium group. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (eg, trimethylene, tetramethylene, pentamethylene, etc.). A hydroxyl group and a C1-C3 alkyl group are mentioned as a substituent.

[0148]

[Chemical 29]

[In the formula, A ₁ , A ₂ , A ₃ and A ₄ may be the same or different and each represents a hydrogen atom, a hydroxyl group, or -C.
OOM, -PO ₃ M _2, represents a -CH ₂ OH or a lower alkyl group (a methyl group, an ethyl group, an isopropyl group, n- propyl group). However, at least one of A ₁ , A ₂ , A ₃ and A ₄ is —COOM or —PO ₃ M ₂ .
M, M ₁ and M ₂ each represent a hydrogen atom, an ammonium group, a sodium atom, a potassium atom, a lithium atom or an organic ammonium group (for example, a trimethylammonium group, a triethanolammonium group, etc.).

[0150]

[Chemical 30]

[In the formula, A _{1 to} A ₄ may be the same or different and each is —CH ₂ OH, —PO ₃ M ₂ or —
Represents COOM. M represents a hydrogen atom, an alkali metal (eg, sodium, potassium) or another cation (eg, ammonium, methylammonium, trimethylammonium, etc.). X is an alkylene group of a substituted or unsubstituted 2-6 carbon atoms _{- (B 1 O) n-} B 2 - represents a.

B ₁ and B ₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms. Examples of the alkylene group represented by X include ethylene, trimemethylene and tetramethylene. Examples of the alkylene group represented by B ₁ and B ₂ include methylene, ethylene, triethylene and the like. Examples of the substituent of the alkylene group represented by X, B ₁ and B ₂ include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, etc.). n is 1
It represents an integer of 8, and is preferably 1 to 4.

Preferred specific examples of the compounds represented by the above general formulas [A], [B] and [C] are shown below.

[0154]

[Chemical 31]

[0155]

[Chemical 32]

[0156]

[Chemical 33]

[0157]

[Chemical 34]

[0158]

[Chemical 35]

[0159]

[Chemical 36]

As the ferric complex salt of the compounds (A-1) to (A-12), a sodium salt, potassium salt or ammonium salt of the second complex salt can be optionally used. From the viewpoint of the effect and solubility of the object of the present invention,
Ammonium salts of these ferric complex salts are preferably used.

Of the above-mentioned compound examples, those particularly preferably used in the present invention include (A-1), (A-3),
(A-4), (A-5), (A-9), (A-10),
(A-11), (B-1), (B-2), (B-6),
(C-1), (C-3) and (C-14), and particularly preferred are (A-1) and (B-2).

The compounds represented by the above formulas [A] to [C] are disclosed in JP-A Nos. 63-267750 and 63-2677.
51, JP-A-2-115172, and JP-A-2-29595.
It can be synthesized by a general synthesis method described in the specification of No. 4 or the like. The amount of the ferric iron complex salt added is preferably in the range of 0.1 to 2.0 mol per liter of the bleaching solution,
The range is more preferably 0.15 to 1.5 mol / liter.

In the bleaching solution or the bleach-fixing solution, preferred bleaching agents other than the iron complex salts of the compounds represented by the above formulas [A] to [C] are described in JP-A-2-302784, page 79, line 1 to page 80. The compounds mentioned in the rows are mentioned. When two or more ferric iron complex salts of organic acids are used in combination, the ferric iron complex salt of the compound represented by the above general formulas [A] to [C] is 70% from the viewpoint that the effect of the present invention is better exhibited. % (Mol equivalent) or more, more preferably 80% or more, and particularly preferably 90%.
It is above, and most preferably 95% or more.

In the bleaching solution or bleach-fixing solution, preferred bleaching agents other than the iron complex salt of the compound represented by the general formula [A] are ferric complex salts of the following compounds (for example, ammonium, sodium, potassium, triethanolamine, etc.). The salt thereof is exemplified, but is not limited thereto.

(A'-1) Ethylenediaminetetraacetic acid (A'-2) Trans-1,2-cyclohexanediaminetetraacetic acid (A'-3) Dihydroxyethylglycine (A'-4) Ethylenediaminetetrakismethylenephosphonic acid (A ''-5) Nitrilotrismethylenephosphonic acid (A'-6) Diethylenetriamine pentakismethylenephosphonic acid (A'-7) Diethylenetriaminepentaacetic acid (A'-8) Ethylenediaminedioltohydroxyphenylacetic acid (A'-9) Hydroxy Ethylethylenediaminetriacetic acid (A'-10) Ethylenediaminedipropionic acid (A'-11) Ethylenediaminediacetic acid (A'-12) Hydroxyethyliminodiacetic acid (A'-13) Nitrilotriacetic acid (A'-14) Nitrilo Tripropionic acid (A'-15) triethyl Tetramine hexaacetic acid (A'-16) ethylenediaminetetraacetic propionic acid

The bleaching solution contains the ferric complex salt of the compound represented by the general formula [A], the above-mentioned (A'-1) to (A'-1).
One or more ferric complex salts of the compound of 6) can be used in combination.

When two or more ferric iron complex salts of organic acids are used in combination, the ferric iron complex salt of the compound represented by the general formula [A] is 70 or more from the viewpoint that the effect of the present invention can be more effectively exhibited. % (Mol conversion) or more,
It is more preferably at least 80%, particularly preferably 90%.
% Or more, and most preferably 95% or more.

The organic acid iron (III) complex salt may be used in the form of a complex salt, or an iron (III) salt such as ferric sulfate, ferric chloride, ferric acetate, ferric ammonium sulfate, An iron (III) ion complex salt may be formed in a solution using ferric phosphate or the like and aminopolycarboxylic acid or a salt thereof.
When used in the form of a complex salt, one type of complex salt may be used, or two or more types of complex salt may be used.

Further, when a complex salt is formed in a solution using a ferric salt and an aminopolycarboxylic acid, one kind or two or more kinds of ferric salts may be used. Furthermore, one or more aminopolycarboxylic acids may be used. or,
In each case, aminopolycarboxylic acid was added to iron (III)
It may be used in excess to form an ionic complex salt. Further, the bleach-fixing solution or bleaching solution containing the above iron (III) ion complex salt may contain a metal ion complex salt of cobalt, copper, nickel, zinc or the like other than iron.

The bleaching solution, the bleach-fixing solution and the fixing solution include imidazole and its derivatives described in JP-A No. 64-295258, compounds represented by the general formulas [I] to [IX] described in the same, and these compounds. By containing at least one of the exemplified compounds of, it is possible to exert an effect on promptness.

In addition to the above accelerators, JP-A-62-1234
Example compounds described on pages 51 to 115 of JP-A No. 59-59, and example compounds described on pages 22 to 25 of JP-A-63-17445, JP-A-53-95630.
The compounds described in JP-A No. 53-28426 and the like can also be used in the same manner.

These accelerators may be used alone or
Two or more kinds may be used in combination, and the addition amount is generally preferably in the range of about 0.01 to 100 g, more preferably 0.05 to 50 g, and particularly preferably 0.05 to 15 g per liter of the bleaching solution. is there. When adding a promoter,
It may be added and dissolved as it is, but it is generally dissolved in water, alkali, organic acid or the like in advance and added, and if necessary, dissolved and added using an organic solvent such as methanol, ethanol or acetone. You can also do it.

The temperature of the bleaching solution or the bleach-fixing solution is 20 to 50.
It is preferably used at 25 ° C, preferably 25-45 ° C. The pH of the bleaching solution is preferably 6.0 or less, more preferably 1.0 or more and 5.5 or less. The pH of the bleach-fixing solution is preferably 5.0 to 9.0, more preferably 6.0 to 8.5. The pH of the bleaching solution or the bleach-fixing solution is the pH of the processing tank when processing the silver halide light-sensitive material.
And can be clearly distinguished from the so-called replenisher pH.

A halide such as ammonium bromide, potassium bromide or sodium bromide is usually added to the bleaching solution or bleach-fixing solution before use. Further, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. The bleaching solution or the bleach-fixing solution may contain other known compounds.

The replenishment amount of the bleaching solution or the bleach-fixing solution is preferably 500 ml or less per 1 m ^{2 of the} silver halide color photographic light-sensitive material, preferably 20 to 400 ml, most preferably 40 to 350 ml. The lower the replenishment amount, the more remarkable the effect of the present invention becomes.

In the present invention, in order to increase the activity of the bleaching solution or the bleach-fixing solution, air or oxygen may be blown in the processing bath and the tank for storing the processing replenisher, if desired, or suitable oxidation may be carried out. Agents, such as hydrogen peroxide,
Bromate, persulfate and the like may be added as appropriate.

As the fixing agent used in the fixing solution or the bleach-fixing solution according to the present invention, thiocyanates and thiosulfates are preferably used. The content of thiocyanate is preferably at least 0.1 mol / liter or more, more preferably 0.3 mol / liter or more, particularly preferably 0.5 mol / liter or more when processing a color negative film. .. The content of thiosulfate is preferably at least 0.2 mol / liter or more, and more preferably 0.5 mol / liter or more when a color negative film is processed.

To the processing solution having fixing ability used in the present invention, it is preferable to add the compound represented by the general formula [FA] described in JP-A 64-295258, page 56, and its exemplified compounds, Not only the effect of the present invention is better exhibited, but also when a small amount of a light-sensitive material is processed for a long period of time, an extremely small amount of sludge is generated in a processing solution having fixing ability.

Good results are obtained when the amount of the compound represented by the general formula [FA] added is in the range of 0.1 to 200 g per liter of the treatment liquid. The processing time with the bleaching solution and the fixing solution according to the present invention is optional, but is preferably 3 minutes and 30 seconds or less, more preferably 10 seconds to 2 minutes and 20 seconds, and particularly preferably 20 seconds to 1 minute 20. It is in the range of seconds. The processing time with the bleach-fixing solution is preferably 4 minutes or less, more preferably 10 seconds to 2 minutes and 20 seconds.

It is preferable as an embodiment of the present invention to apply forced liquid agitation to the stabilizing bath of the treatment method of the present invention. The reason is that not only the effect of the object of the present invention is better achieved, but also the suitability for rapid processing is improved. Here, the forced liquid stirring means that the liquid is not normally diffused and moved, but the liquid is forcibly stirred using a stirring means. As the forced stirring means, there are JP-A 64-222259 and JP-A 1-2.
Means described in each publication such as No. 06343 can be adopted.

Regarding the bleaching solution, JP-A-2-44347.
No., page (3) to page (4) and JP-A-2-435.
No. 46, page (37) to page (38), bleaching agents, pH, acids, and addition amounts of the acids, and ordinary additives such as bleaching accelerators may be used. Ordinary additives such as a fixing agent, a fixing accelerator, a preservative, and a chelating agent described in JP-A-2-44347, page (4) may be used.

A bleach-fixing solution is disclosed in JP-A-2-43546.
The items described in No., page (37) to page (38) may be used. Further, the stabilizing solution according to the present invention includes a bactericide, a fungicide and a chelating agent described in JP-A-2-43546, page (38) to page (39).
A fluorescent whitening agent or the like may be used.

In the silver halide color photographic light-sensitive material used in the present invention, the silver halide emulsion is a
Disclosure 308119 (hereinafter RD30811
9) can be used. The table below shows the locations.

Item RD308119 Page Iodine composition 993 IA Item Production method 993 I-A and 994 E Item Crystal habit Normal crystal 993 I-A Twin crystal 993 I-A Epitaxial 993 I-A Halogen composition Uniform 993 IB term Non-uniform 993 IB term Halogen conversion 994 IC term Halogen substitution 994 IC term Metal-containing 994 ID term Monodisperse 995 IF term Solvent addition 995 IF term Latent image forming position Surface 995 I-G internal 995 I-G applicable photosensitive material Negative 995 I-H positive (including internal fog particles) 995 I-H mixed emulsion 995 I-J desalting Item 995 II-A

In the present invention, the silver halide emulsion is used after physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are
Disclosure No. 17643, No. 1871
6 and No. 308119 (RD17643, respectively
RD18716 and RD308119).

The locations of description are shown below. Item RD308119 RD17643 RD18716 page / page page Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-A-A, B, 23-24 648-9 C, D, H, I, Item J Supersensitizer 996 IV-AE, Item J 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649

Known photographic additives that can be used in the present invention are also described in the above Research Disclosure.
The following table shows the relevant locations.

Item RD308119 RD17643 RD18716 page / page page color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1002 VII-J item 25 Whitening agent 998 V 24 Ultraviolet absorber 1003 VIIIC, 25- 26 XIIIC paragraph light absorber 1003 VIII 25-26 light-scattering agent 1003 VIII filter dye 1003 VIII 25-26 binder 1003 IX 26 651 antistatic 1006 XIII 27 650 agent hardening agent 1004 X 26 651 plasticity 50 X 6 100 6 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Agent Matting agent 1007 XVI Current image agent 1011 XXB Item (included in photosensitive material)

Various couplers can be used in the light-sensitive material used in the present invention, and specific examples thereof are given in the above-mentioned Research Disclosure. The following table shows the relevant locations.

[0190] of the page-item RD17643 items RD308119 th page yellow coupler 1001 VII-D section VII C~G term magenta coupler 1001 VII-D section VII C~G Cyan coupler 1001 VII-D section VII C~G Colored Coupler 1002 VII-G term VII G term DIR coupler 1001 VII-F term VII F term BAR coupler 1002 VII-F term Other useful residues 1001 VII-F term Release coupler Alkali-soluble cap 1001 VII-E term

The additive used in the present invention is RD3081.
It can be added by the dispersion method described in 19XIV. In the present invention, the aforementioned RD17643 is used.
28, RD18716, pages 647-8, and RD3.
The supports described in XVII of 08119 can be used.

For the photosensitive material, the above-mentioned RD308119V is used.
An auxiliary layer such as a filter layer or an intermediate layer described in the section II-K can be provided. The light-sensitive material is a forward layer described in the above-mentioned RD308119VII-K,
Various layer configurations such as an inverse layer and a unit configuration can be adopted.

In the present invention, when the crossover time between the color developing tank and the bleaching tank or the bleach-fixing tank is preferably 10 seconds or less, more preferably 7 seconds or less, the effect different from that of the present invention can be obtained. Effective against certain bleached fog.

The present invention is a color photographic light-sensitive material such as a color paper, a color negative film, a color reversal film, a color reversal paper, a direct positive color paper, a motion picture color film and a television color film which are used for general purposes or for movies. Can be applied to.

[0195]

EXAMPLES Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these. In all the examples below, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

Example 1 One side (surface) of triacetyl cellulose film support
Was subjected to a subbing process, and then the support was sandwiched therebetween, and layers having the following compositions were sequentially formed on the surface (rear surface) opposite to the surface subjected to the subbing process from the support side.

Backside first layer Aluminasol AS-100 (aluminum oxide, manufactured by Nissan Chemical Industries, Ltd.) 100 mg / m ² diacetylcellulose 200 mg / m ² Backside second layer diacetylcellulose 100 mg / m ² stearic acid 10 mg / m ² silica fine particles (Average particle size 0.2 μm) 50 mg / m ^{2 A} multilayer color photographic light-sensitive material 101 was prepared by sequentially forming each layer having the composition shown below from the support side on the surface of a triacetyl cellulose film support which was subjected to an undercoating process. did.

First Layer (Antihalation Layer) Black Colloidal Silver 0.24 g UV Absorber U-1 0.14 g UV Absorber U-2 0.072 g UV Absorber U-3 0.072 g UV Absorber U-4 0.072 g High boiling point solvent O-1 0.31 g High boiling point solvent O-2 0.098 g Poly-N-vinylpyrrolidone 0.15 g Gelatin 2.02 g

Second layer (intermediate layer) High boiling point solvent O-3 0.011 g Gelatin 1.17 g Third layer (low sensitivity red sensitive layer) Spectral sensitized with red sensitizing dyes S-1 and S-2. Silver iodobromide emulsion (3.0 mol% silver iodide, average particle size 0.30 μm) 0.60 g Coupler C-1 0.37 g High boiling point solvent O-2 0.093 g Poly-N-vinylpyrrolidone 0. 074g Gelatin 1.35g

Fourth Layer (Highly Sensitive Red Sensitive Layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes S-1 and S-2 (3.0 mol% silver iodide, average grain size 0) .80 μm) 0.60 g Coupler C-1 0.85 g High boiling point solvent O-2 0.21 g Poly-N-vinylpyrrolidone 0.093 g Gelatin 1.56 g

Fifth layer (intermediate layer) Color mixing inhibitor AS-1 0.20 g High boiling point solvent O-3 0.25 g Matting agent MA-1 0.0091 g Gelatin 1.35 g

Sixth Layer (Low-Sensitivity Green Sensitive Layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye S-3 (3.0 mol% silver iodide, average grain size 0.30 μm) 0 .70 g Coupler M-1 0.31 g Coupler M-2 0.076 g High boiling point solvent O-3 0.059 g Poly-N-vinylpyrrolidone 0.074 g Gelatin 1.29 g

Seventh Layer (Highly Sensitive Green Sensitive Layer) Silver iodobromide emulsion spectrally sensitized with the green sensitizing dye S-3 (3.0 mol% silver iodide, average grain size 0.80 μm) 0 .70 g Coupler M-1 0.80 g Coupler M-2 0.19 g Color mixing inhibitor AS-1 0.055 g High boiling point solvent O-3 0.16 g Poly-N-vinylpyrrolidone 0.12 g Gelatin 1.91 g

Eighth layer (intermediate layer) Gelatin 0.90 g Ninth layer (yellow filter layer) Yellow colloidal silver 0.11 g Color mixing inhibitor AS-1 0.068 g High boiling point solvent O-3 0.085 g Matting agent MA -1 0.012g Gelatin 0.68g

10th Layer (Low Sensitivity Blue Sensitive Layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye S-4 (3.0 mol% silver iodide, average grain size 0.30 μm) 0 .70 g Coupler Y-1 0.86 g Image stabilizer G-1 0.012 g High boiling point solvent O-3 0.22 g Poly-N-vinylpyrrolidone 0.078 g Compound F-1 0.020 g Compound F-2 0.040 g Gelatin 1.09g

Eleventh layer (high-sensitivity blue-sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye S-4 (3.0 mol% silver iodide, average grain size 0.85 μm) 0 .70 g Coupler Y-1 1.24 g Image stabilizer G-1 0.017 g High boiling point solvent O-3 0.31 g Poly-N-vinylpyrrolidone 0.10 g Compound F-1 0.039 g Compound F-2 0.077 g 1.73 g gelatin

Twelfth layer (protective layer-1) Non-photosensitive fine grain silver iodobromide (silver iodide 1.0 mol%, average grain size 0.08 μm) 0.075 g UV absorber U-1 0.048 g UV ray Absorber U-2 0.024g Ultraviolet absorber U-3 0.024g Ultraviolet absorber U-4 0.024g High boiling point solvent O-1 0.13g High boiling point solvent O-2 0.13g Compound F-1 0. 075 g Compound F-2 0.15 g Gelatin 1.2 g

Thirteenth Layer (Protective Layer-2) Sliding Agent WAX-1 0.041 g Matting Agent MA-2 0.0090 g Matting Agent MA-3 0.051 g Surfactant SU-1 0.0036 g Gelatin 0.55 g ( Note: The weight average molecular weight of poly-N-vinylpyrrolidone used in each layer is 350,000.)

The above-mentioned light-sensitive material 101 further comprises gelatin hardeners H-1, H-2, H-3 and water-soluble dye AI-.
1, AI-2, AI-3, compound DI-1, stabilizer ST
-1, Antifoggant AF-1 was appropriately added as needed. The silver halide emulsions used in each light-sensitive layer were all monodisperse emulsions having a distribution of 20% or less.

Each emulsion was desalted and washed with water, and then subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to spectrally sensitize the silver halide emulsion used for each photosensitive layer. To this end, each sensitizing dye, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole was added.

Range of distribution (%) = (standard deviation of particle size / average particle size) × 100

[0212]

[Chemical 37]

[0213]

[Chemical 38]

[0214]

[Chemical Formula 39]

[0215]

[Chemical 40]

[0216]

[Chemical 41]

[0217]

[Chemical 42]

[0218]

[Chemical 43]

After subjecting the photographic material 101 to actual exposure using a camera, a running test was conducted under the following conditions. Treatment process Treatment time Treatment temperature Replenishment amount 1st development 6 minutes 38 ° C. 24 ml Water washing 2 minutes 35-30 ° C. 4 liters / minute Inversion 2 minutes 35 ° C. 12 ml Color development 6 minutes 38 ° C. 24 ml Preparation 2 minutes 35 ° C. 12 ml Drift White 6 minutes 35 ° C 3ml Fixed 4 minutes 35 ° C 12ml Stabilized 5 minutes 30-35 ° C 24ml Dry

However, the stabilization treatment was carried out in a three-tank counter current so that the final tank of the stabilizing solution was replenished and the overflow was introduced into the previous tank. (The replenishment amount is the value per 100 cm ^{2 of} the light-sensitive material, excluding the washing step.)
The composition of the treatment liquid used in the above treatment step is as follows.

[First Development Replenisher] Diethylenetriamine pentaacetic acid 3 g Sodium sulfite 20 g Hydroquinone monosulfonate 22 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Sodium bromide 1.4 g Potassium thiocyanate 1.0 g Potassium iodide 1.5 mg Water is added to make 1 liter, and the pH is adjusted to 9.65.

[First Developer] Diethylenetriamine pentaacetic acid 3 g Sodium sulfite 20 g Hydroquinone monosulfonate 22 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Sodium bromide 2 .2 g Potassium thiocyanate 1.0 g Potassium iodide 4.5 mg Water is added to make 1 liter and the pH is adjusted to 9.60.

[Inversion tank liquid and inversion replenisher] Propionic acid 12.0 ml Stannous chloride 1.65 g p-Aminophenol 0.5 mg Diethylenetriamine pentaacetic acid 10 g Sodium hydroxide 4.8 g Water was added to make 1 liter, The pH is set to 5.75.

[Color developer] Diethylenetriamine pentaacetic acid 3 g Phosphoric acid (85% aqueous solution) 8.7 ml Potassium hydroxide (45% aqueous solution) 40 ml Sodium sulfite 4.5 g Citrazinic acid 1.5 g N-ethyl-N-β-mentor Sulfonamidoethyl-3-methyl-4-aminoaniline / sulfate 11 g 2,2-ethylenedithiodiethanol 1.0 g Sodium bromide 0.65 g Potassium iodide 30 mg Water is added to bring the pH to 11.70. ..

[Color development replenisher] Diethylenetriamine pentaacetic acid 3 g Phosphoric acid (85% aqueous solution) 8.7 ml Potassium hydroxide (45% aqueous solution) 40 ml Sodium sulfite 4.5 g Citrazic acid 1.5 g N-ethyl-N-β- Mentasulfonamidoethyl-3-methyl-4-aminoaniline / sulfate 11 g 2,2-ethylenedithiodiethanol 1.0 g Water is added to adjust the pH to 11.95.

[Preparation tank solution and adjusted replenisher solution] Potassium sulfite 10 g Ethylenediaminetetraacetic acid 8.0 g β-mercaptopropionic acid 0.5 g Water is added to adjust the pH to 6.15.

[Bleaching Replenisher] Potassium nitrate 50 g Potassium bromide 156 g Ethylenediaminetetraacetic acid iron (III) 250 g Water is added to make 1 liter and pH is 5.45.

[Bleaching Solution] Potassium nitrate 25 g Potassium bromide 78 g Ethylenediaminetetraacetic acid iron (III) 125 g Water is added to adjust the pH to 5.65.

[Fixing Tank Solution and Fixing Replenisher] Ammonium thiosulfate 80 g Sodium sulfite 5 g Sodium bisulfite 5 g Water is added to make 1 liter and pH is 6.60.

[Stabilizing Solution and Stable Replenishing Solution] Benzisothiazolin-3-one 0.05 g Surfactant (Exemplified Compound I-5) 0.5 g Compound of general formula [F] or comparative compound (described in Table 1) Water To 1 liter and adjust the pH to 8.5.

The running treatment was carried out until the amount of the stable replenisher solution which was twice the capacity of the stable tank tank was replenished (0.
07R (R = total amount of replenisher / tank volume)) A small running experiment developing machine was used.

The magenta density of the highest density portion of the processed film sample after the running processing was measured, and then 75
The dye was stored for 2 weeks at a temperature of 20 ° C and a relative humidity of 20%, and the maximum density of magenta after storage was measured to obtain the fading rate of the dye.

Further, the sample was stored at 75 ° C. and 60% relative humidity for 1 week, and the yellow density of the unexposed area was measured to obtain yellow stain. Further, 1 liter of the liquid in the stabilizing tank was stored at 35 ° C. in a beaker having an opening area of 10 cm ² to evaluate the stability of the liquid (the number of days until sulfation). The results are summarized in Table 4.

[0234]

[Table 4]

As is clear from the results shown in Table 4, when formaldehyde is used, the dye image storability and yellow stain are very excellent, but Experiment N which is a comparative example.
o. In 1-1 to 1-3, it is found that the stability of the stabilizing solution is very poor. On the other hand, the experiment No. 1-4
It can be seen that the storage stability of the stabilizing solution is remarkably excellent in the range of 1 to 22.

Example 2 After subjecting the film sample used in Example 1 to actual exposure using a camera, a running test was conducted under the following conditions.

Treatment Step Treatment Time Treatment Temperature Replenishment Amount 1st development 6 minutes 38 ° C. 24 ml Water wash 2 minutes 30-35 ° C. 4 liter / min Inversion 2 minutes 35 ° C. 12 ml Color development 6 minutes 38 ° C. 24 ml Preparation 2 minutes 35 ℃ 12ml Bleach 6 minutes 35 ℃ 3ml Fixing 4 minutes 35 ℃ 12ml Washing water 4 minutes 35 ℃ 4 liters / minute Stability 2 minutes 30-35 ℃ 24ml Dry (Replenishing amount is 100 cm of light-sensitive material It is a value per ^2. )

The running treatment was carried out until the amount of the stable replenisher solution which was twice the capacity of the stable tank tank was replenished (0.
07R (R = total amount of replenisher / tank volume)) A small running experiment developing machine was used.

After the running treatment, the magenta density of the highest density part of the processed film sample was measured, and then 75
The dye was stored for 2 weeks at a temperature of 20 ° C and a relative humidity of 20%, and the maximum density of magenta after storage was measured to obtain the fading rate of the dye.

Further, the sample was stored for 1 week at 75 ° C. and 60% relative humidity, and the yellow density of the unexposed area was measured to obtain yellow stain. The same processing solution and replenishing solution as in Example 1 were used. The results are summarized in Table 5.

[0241]

[Table 5]

As is clear from the results in Table 5, it is found that the compound represented by the general formula [F] according to the present invention exhibits good fading rate and yellow stain. Of course, the stability of the stabilizing solution is also good.

Example 3 The hardener H-2 in the film sample prepared in Example 1 was the hardener H-2 shown in Table 3 below, and the others were the same as Experiment N of Example 1.
o. The experiment was conducted in the same manner as 1 to 5. The evaluation criteria were set as follows.

(1) Occurrence of Film Stain: ∘ None. △ There are a few, but there is no problem as a product. × Inappropriate for the product. (2) Scratch scratch occurrence: ∘ None. △ There are a few, but there is no problem as a product. × Inappropriate for the product. The above results are shown in Table 6.

Table 6 Experiment No. Hardener Film Stain Magenta occurrence of scratches Occurrence status Stain 3-1 Example (VS-6) ○ ○ 0.00 3-2 Example (VS-9) ○ ○ 0.01 3-3 Example (VS-) 10) ○ △ to ○ 0.00 3-4 Examples (VS-12) ○ ○ 0.00 3-5 Examples (VS-22) ○ ○ 0.01 3-6 Examples (VS-33) △ to ○ ○ 0.00 3-7 Example (VS-54) △ to ○ ○ 0.01 3-8 Following RH-1 △ △ to ○ 0.01 3-9 Following RH-2 △ to × △ to ○ 0.023 -10 Following RH-3 △ ○ 0.02 3-11 Following RH-4 △ △ ~ ○ 0.02 3-12 Following RH-5 △ △ ~ ○ 0.02

[0246]

[Chemical 44]

As is clear from Table 6, when the vinyl sulfonic acid type hardener is used in combination with the treatment method of the present invention, the effect of the present invention can be obtained, and in addition, stains and scratches on the film can be obtained. It can be seen that there is no occurrence of.

Example 4 The following fixing solution was prepared. Ammonium thiosulfate 200 g Anhydrous sodium bisulfite 20 g Sodium metabisulfite 4.0 g Ethylenediaminetetraacetic acid disodium 1.0 g Urea 1.0 g Exemplified compounds (listed in table 6) (listed in table 6)

Water is added to make 1 liter, and the pH is adjusted to 6.5 using glacial acetic acid and aqueous ammonia. After adjustment, store in a 1 liter beaker with an opening area of 10 cm ² at 30 ° C,
The number of days until precipitation due to sulfurization was evaluated. The results are shown in Table 6.

[Table 6] Fixer Solution Additive Solution storability ( number of days until sulfuration occurs No. (amount added per liter )) Remarks 1-1 Formaldehyde (35%) 7 days Comparative Example 4.0 ml 1 -2 Hexamethylenetetramine 3.0g 10 days Comparative example 1-3 Dimethylol urea 2.0g 8 days Comparative example 1-3 Acetaldehyde 2.0g 9 days Comparative example 1-4 Exemplified compound (F-1) 2.0g 32 days Present Invention 1-5 Exemplified Compound (F-2) 2.0 g 33 days Present Invention 1-6 Exemplified Compound (F-3) 2.0 g 35 days Present Invention 1-7 Exemplified Compound (F-4) 2.0 g 34 Day Present Invention 1-8 Exemplified Compound (F-6) 2.0 g 32 days Present Invention 1-9 Exemplified Compound (F-10) 2.0 g 30 days Present Invention 1-10 Exemplified Compound (F-13) 2.0 g 31st Invention 1-11 Examples Compound (F-23) 2.0 g 31 days Present invention 1-12 Exemplified compound (F-24) 2.0 g 30 days Present invention 1-13 Exemplified compound (F-37) 2.0 g 29 days Present invention 1- 14 Exemplified compound (F-46) 2.0 g 33 days Present invention 1-15 Exemplified compound (F-48) 2.0 g 30 days Present invention 1-16 Exemplified compound (F-51) 2.0 g 28 days Present invention 1 -17 Exemplified Compound (F-59) 2.0 g 26 days Present Invention 1-18 Exemplified Compound (F-61) 2.0 g 30 days Present Invention

As is clear from Table 6, the fixability of formaldehyde-added fixer 1-1 is extremely poor in storage stability, and fixers 1-2 to 1-4 using the conventional formaldehyde substitute compounds also have the effect of keeping the solution stable. Shelf life is not good. On the other hand, fixing solutions 1-6 to 1-1 using the compound of the present invention
All of 9 have good liquid storability.

Example 5 The following preparation solution was prepared. Anhydrous ammonium bisulfite 10 g EDTA 8.0 g β-mecaptopyropionic acid 0.5 g Exemplified compound (described in Table 7) Amount described in Table 7 Water is added to make 1 liter and pH is 6.15.

After the adjustment, the mixture was stored in a 1 liter beaker having an opening area of 10 cm ² at 30 ° C. for 2 weeks, and the degree of scum generation was evaluated using the following symbols. The results are shown in Table 7.

[Evaluation Criteria] ○ No scum generation △ Slight scum generation × Scum generation

[Table 7] Conditioning liquid Additives Liquid storability No. (Addition amount per liter) Degree of scum Remark 2-1 None × Comparison 2-2 Formaldehyde (35%) △ Comparison 4.0 ml △ Comparison 2-3 Hexamethylenetetramine 3.0 g △ ~ × Comparison 2- 4 Dimethylol urea 2.0 g △ Comparison 2-5 Acetaldehyde 2.0 g ○ Present invention 2-6 Exemplified compound (F-1) 2.0 g ○ Present invention 2-7 Exemplified compound (F-2) 2.0 g ○ Present invention 2-8 Exemplified compound (F-3) 2.0 g Present invention 2-9 Exemplified compound (F-4) 2.0 g Present invention 2-10 Exemplified compound (F-6) 2.0 g Present invention 2- 11 Exemplified Compound (F-10) 2.0 g ○ Present Invention 2-12 Exemplified Compound (F-13) 2.0 g ○ Present Invention 2-13 Exemplified Compound (F-23) 2.0 g ○ Present Invention 2-14 Exemplified Compound (F-24) 2.0 g ○ to △ Invention 2-15 Exemplified Compound (F-37) 2.0 g ○ Invention 2-16 Exemplified Compound (F-46) 2.0 g ○ Invention 2-17 Exemplified Compound (F-48) 2. 0 g ◯ to Δ Present invention 2-18 Exemplified compound (F-51) 2.0 g Present invention 2-19 Exemplified compound (F-59) 2.0 g Present invention 2-20 Exemplified compound (F-61) 2. 0g ○ The present invention

As is clear from Table 7, the prepared liquids containing formaldehyde and conventional formaldehyde-replacement compounds have poor storage stability. On the other hand, all of the adjustment liquids using the compound according to the present invention have good liquid storability.

Example 6 The following preliminary washing water was prepared. 2-Methyl-4-isothiazolin-3-one 0.1 g EDTA 1.0 g Exemplified compounds (described in Table 8) Amount described in Table 8 Fixer (* 1) 20 ml Water was added to 1 liter to adjust the pH to 6.0. Adjusted to.

After the adjustment, the beaker was stored in a 1 liter beaker with an opening area of 10 cm ² at 30 ° C., and the number of days until precipitation was caused by sulfurization was evaluated. The results are shown in Table 8. (* 1) The fixer has the following composition. Ammonium thiosulfate 120 g Ammonium sulfite 5 g Silver bromide 7 g Water was added to make 1 liter, and the pH was adjusted to 7.0 with ammonium hydroxide or glacial acetic acid.

[Table 8] Preliminary rinsing water addition Additive liquid storability No. (Amount added per liter) ( Number of days until remark that sulfurization occurs) 3-1 Formaldehyde (35%) 4.0 ml <1 day Comparison 3-2 Hexamethylenetetramine 3.0 g 3 days Comparison 3-3 Acetaldehyde 2 0.0 g 3 days Comparison 3-4 Dimethylol urea 2.0 g 2 days Comparison 3-5 Exemplified compound (F-1) 2.0 g 8 days Present invention 3-6 Exemplified compound (F-2) 2.0 g 9 days Present invention 3-7 Exemplified Compound (F-3) 2.0 g 10 days Present Invention 3-8 Exemplified Compound (F-4) 2.0 g 8 days Present Invention 3-9 Exemplified Compound (F-6) 2.0 g 9 days Present Invention 3-10 Exemplified compound (F-10) 2.0 g 7 days Present invention 3-11 Exemplified compound (F-13) 2.0 g 8 days Present invention 3-12 Exemplified compound (F-23) 2.0 g 8 days Present Invention 3-13 Exemplified Compound (F-2 ) 2.0 g 7 days Present invention 3-14 Exemplified compound (F-37) 2.0 g 7 days Present invention 3-15 Exemplified compound (F-46) 2.0 g 6 days Present invention 3-16 Exemplified compound (F- 48) 2.0 g 8 days Present invention 3-17 Exemplified compound (F-51) 2.0 g 8 days Present invention 3-18 Exemplified compound (F-59) 2.0 g 5 days Present invention 3-19 Exemplified compound (F -61) 2.0 g 8 days The present invention

As is apparent from Table 8, the prewash water 3-1 with the addition of the fumaldehyde has a markedly poor storability, and the prewash water 3-2 to 3-4 using the conventional formaldehyde substitute is used. Also, the storage stability of the solution is not good. On the other hand, preliminary washing water 3-6 to 3 using the compound of the present invention
All of -19 have good liquid storage stability.

Example 7 Multilayer color photographic light-sensitive material 101 produced in Example 1
Was subjected to actual exposure using a camera, and a running test was performed under the following conditions.

Treatment step Treatment time Treatment temperature Replenishment amount First development 6 minutes 38 ° C. 24 ml Water washing 2 minutes 35 to 30 ° C. 4 liter / min Inversion 2 minutes 35 ° C. 12 ml Color development 6 minutes 38 ° C. 24 ml Adjustment 2 minutes 35 ℃ 12ml Bleach 6 minutes 35 ℃ 3ml Settling 4 minutes 35 ℃ 12ml Water wash 4 minutes 30-35 ℃ 4 liters / minute Stability 1 minute 30-35 ℃ 24ml Dry

However, the stabilization treatment was carried out by a three-tank counter current method in which the final tank of the stabilizing solution was replenished and overflow was introduced into the previous tank. (The replenishment amount is the value per 100 cm ^{2 of} the light-sensitive material, excluding the washing step.)
The composition of the treatment liquid used in the above treatment step is as follows.

[First Development Replenisher] Diethylenetriamine pentaacetic acid 3 g Sodium sulfite 20 g Hydroquinone monosulfonate 22 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Sodium bromide 1.4 g Potassium thiocyanate 1.0 g Potassium iodide 1.5 mg Water is added to make 1 liter, and the pH is adjusted to 9.65.

[First Developer] Diethylenetriamine pentaacetic acid 3 g Sodium sulfite 20 g Hydroquinone monosulfonate 22 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Sodium bromide 2 .2 g Potassium thiocyanate 1.0 g Potassium iodide 4.5 mg Water is added to make 1 liter and the pH is adjusted to 9.60.

[Inversion tank liquid and inversion replenisher] Propionic acid 12.0 ml Stannous chloride 1.65 g p-Aminophenol 0.5 mg Diethylenetriamine pentaacetic acid 10 g Sodium hydroxide 4.8 g Water was added to make 1 liter, The pH is set to 5.75.

[Color developer] Diethylenetriamine pentaacetic acid 3 g Phosphoric acid (85% aqueous solution) 8.7 ml Potassium hydroxide (45% aqueous solution) 40 ml Sodium sulfite 4.5 g Citrazic acid 1.5 g N-ethyl-N-β-mentor Sulfonamidoethyl-3-methyl-4-aminoaniline / sulfate 11 g 2,2-ethylenedithiodiethanol 1.0 g Sodium bromide 0.65 g Potassium iodide 30 mg Water is added to bring the pH to 11.70. ..

[Color development replenisher] diethylenetriamine pentaacetic acid 3 g phosphoric acid (85% aqueous solution) 8.7 ml potassium hydroxide (45% aqueous solution) 40 ml sodium sulfite 4.5 g citrazinic acid 1.5 g N-ethyl-N-β- Mentasulfonamidoethyl-3-methyl-4-aminoaniline / sulfate 11 g 2,2-ethylenedithiodiethanol 1.0 g Water is added to adjust the pH to 11.95.

[Adjustment Tank Solution and Adjustment Replenisher] Potassium sulfite 10 g Ethylenediaminetetraacetic acid 8.0 g β-Mercaptopropionic acid 0.5 g Water is added to make 1 liter and pH is 6.15.

[Bleach Replenisher] Potassium nitrate 50 g Potassium bromide 156 g Ethylenediaminetetraacetic acid iron (III) 250 g Water is added to adjust the pH to 5.45.

[Bleaching Solution] Potassium nitrate 25 g Potassium bromide 78 g Ethylenediaminetetraacetic acid iron (III) 125 g Water is added to adjust the pH to 1.65.

[Fixing Tank Solution and Fixing Replenisher] Ammonium thiosulfate 180 g Sodium sulfite 10 g Sodium bisulfite 5 g Compound of general formula F or comparative compound (described in Table 9) The amount described in Table 9 is added to 1 liter, The pH is set to 6.60.

[Stabilizing Solution and Stabilizing Replenishing Solution] Benzisothiazolin-3-one 0.05 g Surfactant (Exemplified Compound I-5) 0.5 g Water is added to adjust the pH to 8.5.

The running treatment was carried out until the amount of the fixing replenisher solution that was twice the capacity of the fixing tank tank was replenished (0.
07R (R = total amount of replenisher / tank volume)) A small running experiment developing machine was used.

The magenta density of the highest density portion of the processed film sample after the running processing was measured, and then 75
The dye was stored for 2 weeks at a temperature of 20 ° C and a relative humidity of 20%, and the maximum density of magenta after storage was measured to obtain the fading rate of the dye.

Further, it was stored for 1 week at 75 ° C. and 60% relative humidity, and the yellow density of the unexposed area was measured to obtain yellow stain. Furthermore, 1 liter of the liquid in the fixing tank was stored in a beaker having an opening area of 10 cm ² at 35 ° C., and the stability of the liquid (the number of days until sulfuration) was evaluated. The results are summarized in Table 9.

[0277]

[Table 9]

As is clear from the results shown in Table 9, when formaldehyde is used, the dye image storability and yellow stain are very excellent, but Experiment N which is a comparative example.
o. In Nos. 1-1 to 1-3, it can be seen that the fixability of the fixer is very poor. On the other hand, the experiment No. 1-4
It can be seen that the storage stability of the fixer is markedly excellent in the range of 1 to 22.

Example 8 After subjecting the photosensitive material 101 prepared in Example 1 to actual exposure using a camera, a running test was conducted under the same conditions as in Example 7. However, the adjustment tank liquid and the adjustment replenisher, and the fixing tank liquid and the fixing replenisher were changed as follows.

[Preparation Tank Solution and Preparation Replenisher] Potassium sulfite 10 g Ethylenediaminetetraacetic acid 8.0 g β-Mercaptopropionic acid 0.5 g Compound of general formula F or comparative compound (described in Table 10) Adjust to liter and pH 6.15.

[Fixing Tank Solution and Fixing Replenisher] Ammonium thiosulfate 180 g Sodium sulfite 10 g Sodium bisulfite 5 g Water is added to adjust the pH to 6.60.

The running treatment was carried out until the amount of the adjustment replenisher solution which was twice the volume of the adjustment tank tank was replenished (0.
07R (R = total amount of replenisher / tank volume)) A small running experiment developing machine was used.

The magenta density of the highest density portion of the processed film sample after the running processing was measured, and then 75
The dye was stored for 2 weeks at a temperature of 20 ° C and a relative humidity of 20%, and the maximum density of magenta after storage was measured to obtain the fading rate of the dye.

Further, the sample was stored for 1 week at 75 ° C. and 60% relative humidity, and the yellow density of the unexposed area was measured to determine the yellow stain. Further, 1 liter of the liquid in the adjusting tank was stored at 35 ° C. in a beaker having an opening area of 10 cm ² , and the stability of the liquid (the degree of scum generation) was evaluated. The results are summarized in Table 10.

[0285]

[Table 10]

As is clear from the results shown in Table 10, when formaldehyde is used, the dye image storability and yellow stain are very excellent, but the results of Experiment No. In 1-1 to 1-3, it can be seen that the storability of the adjusted liquid is poor. On the other hand, the experiment No. 1-4-1
It can be seen that with -22, the storage stability of the adjustment liquid is remarkably excellent.

Example 9 In this example, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.
A multilayer color photographic light-sensitive material sample 102 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

Sample 102 First Layer: Antihalation Agent Black Colloidal Silver 0.18 UV Absorber (UV-1) 0.20 Colored Coupler (CC-1) 0.05 Colored Coupler (CM-2) 0.06 High Boiling point solvent (Oil-1) 0.20 Gelatin 1.5

Second layer: intermediate layer Ultraviolet absorber (UV-1) 0.01 High boiling point solvent (Oil-1) 0.01 Gelatin 1.2

Third layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0.9 Silver iodobromide emulsion (Em-2) 0.6 Sensitizing dye (S-1) 2.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.5 × 10 ^-4 (mol / Silver 1 mol) Cyan coupler (C-4 ') 1.2 Cyan coupler (C-2') 0.3 Colored cyan coupler (CC-1) 0.05 DIR compound (D-1) 0.002 High boiling point Solvent (Oil-1) 0.5 Gelatin 1.2

Fourth layer: High-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Em-3) 2.0 Sensitizing dye (S-1) 2.2 × 10 ⁻⁴ (mol / silver 1 mol) Sensitization Dye (S-2) 2.0 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-1 ′) 0.20 Cyan coupler (C-2 ') 0.03 Cyan coupler (C-3') 1.15 Colored cyan coupler (CC-1) 0.015 DIR compound (D-2) 0.05 High boiling point solvent ( Oil-1) 0.5 Gelatin 1.3 Fifth layer: Intermediate layer Gelatin 0.5

Sixth Layer: Low Sensitivity Green Sensitive Emulsion Layer Silver iodobromide emulsion (Em-1) 1.1 Sensitizing dye (S-4) 5 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye ( S-5) 2 × 10 ⁻⁴ (mol / silver 1 mol) Magenta coupler (M-1) 0.45 Colored magenta coupler (CM-1) 0.05 DIR compound (D-3) 0.015 DIR compound ( D-4) 0.020 High boiling point solvent (Oil-2) 0.5 Gelatin 1.0

Seventh layer: intermediate layer Gelatin 0.9 High boiling point solvent (Oil-1) 0.2

Eighth layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Em-3) 1.2 Sensitizing dye (S-6) 1.5 × 10 ⁻⁴ (mol / silver 1 mol) Sensitization Dye (S-7) 2.5 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing Dye (S-8) 0.7 × 10 ⁻⁴ (mol / silver 1 mol) Magenta Coupler (M-2) 0 0.08 Magenta coupler (M-3) 0.18 Colored magenta coupler (CM-2) 0.05 DIR compound (D-3) 0.01 High boiling point solvent (Oil-3) 0.5 Gelatin 1.3

Ninth layer: Yellow filter layer Yellow colloidal silver 0.12 Color stain inhibitor (SC-1) 0.1 High boiling point solvent (Oil-3) 0.1 Gelatin 0.8

Layer 10: Low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0.30 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (S-10) 7 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.6 Yellow coupler (Y-2) 0.2 DIR compound (D-2) 0.01 High boiling point solvent (Oil-3) 0.15 Gelatin 1.2

Eleventh layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-4) 0.50 Silver iodobromide emulsion (Em-1) 0.22 Sensitizing dye (S-9) 1.3 × 1. ^-4 (mol / silver 1 mol) Sensitizing dye (S-10) 3 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.36 Yellow coupler (Y-2) 0.12 High Boiling point solvent (Oil-3) 0.07 Gelatin 1.2

Twelfth Layer: First Protective Layer Fine grain silver iodobromide emulsion (average particle size 0.08 μm, AgI content 2.5 mol%) 0.40 UV absorber (UV-1) 0.10 UV absorption Agent (UV-2) 0.05 High-boiling point solvent (Oil-1) 0.1 High-boiling point solvent (Oil-4) 0.1 Formalin skabesha (HS-1) 0.5 Formalin sukabesha (HS-2) 0.2 gelatin 1.2

Thirteenth layer: Second protective layer Surfactant (Su-1) 0.005 Alkali-soluble matting agent (average particle size 2 μm) 0.10 Cyan dye (AIC-1) 0.01 Magenta dye ( AIM-1) 0.01 Sliding agent (WAX-1) 0.04 Gelatin 0.7

In each layer, in addition to the above composition, coating aid Su-2, dispersion aid Su-3, preservative DI-1, stabilizer Stab-1, antifoggant AF-1, AF-. 2 was added. Em-1 Average grain size 0.46 µm Average silver iodide content 7.0 mol%, monodisperse surface low silver iodide-containing emulsion Em-2 Average grain size 0.32 µm Average silver iodide content 2. 5 mol%, monodisperse emulsion of uniform composition

Em-3 Average grain size 0.78 μm Average silver iodide content 6.0 mol%, monodisperse surface low silver iodide-containing emulsion Em-4 Average grain size 0.95 μm Average silver iodide content Emulsion containing surface low silver iodide having a rate of 7.5 mol%

Em-1, Em-3 and Em-4 have a multi-layer structure adjusted with reference to JP-A-60-138538 and JP-A-61-245151, and iodobromide mainly composed of octahedron. It is a silver emulsion. In addition, Em-1 to Em-
In all 4, the average value of particle size / particle thickness is 1.0, and the width of particle distribution is 14%, 10% and 12 respectively.
% And 12%.

[0303]

[Chemical 45]

[0304]

[Chemical 46]

[0305]

[Chemical 47]

[0306]

[Chemical 48]

[0307]

[Chemical 49]

[0308]

[Chemical 50]

[0309]

[Chemical 51]

[0310]

[Chemical 52]

[0311]

[Chemical 53]

[0312]

[Chemical 54]

[0313]

[Chemical 55]

The film sample thus produced was subjected to actual exposure using a camera, and then a running test was conducted under the following conditions.

Treatment step Treatment step Treatment time Treatment temperature Replenishment amount Color development 3 minutes 15 seconds 38 ° C. 775 ml Bleach 3 minutes 15 seconds 38 ° C. 300 ml settling 3 minutes 15 seconds 38 ° C. 500 ml Prewash 1 minute 30 seconds 35 ° C. 450 ml Water Washing 3 minutes 30 seconds 35 ° C. to 38 ° C. 4 liters / minute Stabilization 1 minute 38 ° C. 775 ml Drying 1 minute 40 ° C. to 70 ° C. (Replenishment amount is a value per 1 m ² of the light-sensitive material.)

However, the stabilization treatment was carried out by a counter current of two tanks, and an overflow was made to flow into the previous tank which was supplemented to the final tank of the stabilizing solution.

[Color developer] Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.2 g Potassium iodide 0.6 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino- 3-Methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.6 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to make 1 liter and potassium hydroxide or 20
Adjust to pH 10.01 with% sulfuric acid.

[Color development replenisher] potassium carbonate 40 g sodium hydrogen carbonate 3 g potassium sulfite 7 g sodium bromide 0.5 g hydroxylamine sulfate 3.1 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxy Ethyl) aniline sulfate 6.0 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 2 g Water to make 1 liter, potassium hydroxide or 20%
Adjust to pH 10.12 with sulfuric acid.

[Bleach] 1,3-Diaminopropanetetraacetic acid ferric ammonium 0.20 g Ethylenediaminetetraacetic acid disodium 10 g Ammonium bromide 100 g Glacial acetic acid 40 g Ammonium nitrate 40 g Water was added to make 1 liter, and aqueous ammonia or glacial acetic acid was added. Adjust to pH 4.4 using.

[Bleach Replenisher] 1,3-Propylenediaminetetraacetic acid ferric ammonium 0.25 g Ethylenediaminetetraacetic acid disodium 2 g Ammonium bromide 120 g Ammonium nitrate 50 g Glacial acetic acid 40 g Water was added to make 1 liter and ammonia water or Adjust to pH 3.4 with glacial acetic acid.

[Fixer and fixer replenisher] Ammonium thiosulfate 150 g Anhydrous sodium bisulfite 20 g Sodium metabisulfite 4.0 g Ethylenediaminetetraacetic acid disodium 1.0 g Urea 1.0 g Water was added to make 1 liter, and glacial acetic acid and ammonia were added. Adjust to pH 6.5 with water.

[Preliminary Washing Solution and Preliminary Washing Replenisher] 2-Methyl-4-isothiazolin-3-one 0.1 g Ethylenediaminetetraacetic acid 1.0 g Compound of general formula F or comparative compound (described in Table 11) Add water to make 1 liter and adjust the pH to 6.15.

[Stabilizing Solution and Stabilizing Replenishing Solution] Benzisothiazol-3-one 0.05 g Surfactant (Exemplified Compound I-5) 0.5 g Water is added to adjust the pH to 8.5.

The running treatment was carried out until the preliminary washing replenisher solution having a volume twice that of the preliminary washing tank tank was replenished (0.07 R per day (R = total replenisher solution / tank volume)). I went by machine.

After the running treatment, the magenta density of the highest density portion of the processed film sample was measured, and then 75
The dye was stored for 2 weeks at a temperature of 20 ° C and a relative humidity of 20%, and the maximum density of magenta after storage was measured to obtain the fading rate of the dye.

Further, it was stored for 1 week at 75 ° C. and 60% relative humidity, and the yellow density of the unexposed area was measured to obtain yellow stain. Furthermore, 1 liter of the liquid from the preliminary water washing tank was stored in a beaker having an opening area of 10 cm ² at 35 ° C, and the stability of the liquid (the number of days until sulfidation) was evaluated. The results are summarized in Table 1
Shown in 1.

[Table 11]

[0327]

As is clear from the results shown in Table 11, when formaldehyde is used, the dye image storability and yellow stain are very excellent, but Experiment No. It is understood that in 1-1 to 1-3, the preservability of the preliminary washing solution is very poor. On the other hand, the experiment No.
In 1-4 to 1-15, it is understood that the preservability of the preliminary washing solution is remarkably excellent.

Example 10 The same test as in Example 9 was conducted except that the treatment process and the treatment liquid were changed as follows.

Processing step Processing time Processing temperature Replenishment amount Color development 3 minutes 15 seconds 38 ° C. 775 ml Bleach 45 seconds 38 ° C. 155 ml Settling 1 minute 30 seconds 38 ° C. 500 ml Stabilization 50 seconds 38 ° C. 775 ml Dry 1 minute 40 ° C. 70 ° C .- (Replenishment amount is a value per 1 m ² of light-sensitive material.)

However, the stabilization treatment was carried out by a two-tank counter current, and the stabilizing solution was replenished in the final tank and overflowed into the previous tank.

[Color developer] Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.2 g Potassium iodide 0.6 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino- 3-Methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.6 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to make 1 liter and potassium hydroxide or 20
Adjust to pH 10.01 with% sulfuric acid.

[Color development replenisher] potassium carbonate 40 g sodium hydrogen carbonate 3 g potassium sulfite 7 g sodium bromide 0.5 g hydroxylamine sulfate 3.1 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxy Ethyl) aniline sulfate 6.0 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 2 g Water to make 1 liter, potassium hydroxide or 20%
Adjust to pH 10.12 with sulfuric acid.

[Bleach] 1,3-Diaminopropanetetraacetic acid ferric ammonium 0.32 mol Ethylenediaminetetraacetic acid disodium 10 g Ammonium bromide 100 g Glacial acetic acid 40 g Ammonium nitrate 40 g Water was added to make 1 liter, and ammonia water or ice was added. Adjust to pH 4.4 with acetic acid.

[Bleaching Replenisher] 1,3-Propylenediaminetetraacetic acid ferric ammonium 0.35 g Ethylenediaminetetraacetic acid disodium 2 g Ammonium bromide 120 g Ammonium nitrate 50 g Glacial acetic acid 40 g Water was added to make 1 liter, and ammonia water or Adjust to pH 3.4 with glacial acetic acid.

[Fixer and fixer replenisher] Ammonium thiosulfate 150 g Anhydrous sodium bisulfite 20 g Sodium metabisulfite 4.0 g Ethylenediaminetetraacetic acid disodium 1.0 g Urea 1.0 g Water was added to 1 liter, and glacial acetic acid and ammonia were added. Adjust to pH 6.5 with water.

[Preliminary Washing Solution and Preliminary Washing Replenisher] 2-Methyl-4-isothiazolin-3-one 0.1 g Ethylenediaminetetraacetic acid 1.0 g Compound of general formula F or comparative compound (described in Table 12) Add water to make 1 liter and adjust the pH to 6.15.

[Stabilizing Solution and Stabilizing Replenishing Solution] Benzisothiazol-3-one 0.05 g Surfactant (Exemplified Compound I-5) 0.5 g Water is added to adjust the pH to 8.5.

The running treatment was carried out until development of a small-sized running experiment was carried out until the amount of the preliminary washing replenisher solution twice the volume of the preliminary washing tank tank was replenished (0.07 R per day (R = total replenisher solution volume / tank volume)). I went by machine.

The magenta density of the highest density portion of the processed film sample after the running processing was measured, and then 75
The dye was stored for 2 weeks at a temperature of 20 ° C and a relative humidity of 20%, and the maximum density of magenta after storage was measured to obtain the fading rate of the dye.

Further, it was stored at 75 ° C. and 60% relative humidity for 1 week, and the yellow density of the unexposed area was measured to obtain yellow stain. Further, 1 liter of the liquid in the adjusting tank was stored at 35 ° C. in a beaker having an opening area of 10 cm ² to evaluate the stability of the liquid (the number of days until sulfation). The results are summarized in Table 12
Shown in.

[0342]

[Table 12]

As is clear from the results in Table 12, the dye image storability and the yellow stain are excellent and the prewash water storability is excellent by using the compound according to the present invention even in rapid processing. ..

[0344]

INDUSTRIAL APPLICABILITY In the processing method of a silver halide color photographic light-sensitive material for forming a silver halide color reversal image as in the present invention, even if formaldehyde is not contained in the stabilizing solution, it is represented by the general formula [F]. The inclusion of these compounds prevents the occurrence of dye fading and yellow stains in image storage under low humidity, and further improves the scratch resistance of color reversal photographic light-sensitive materials by adding a vinyl sulfonic acid type hardener. In addition, it is excellent in liquid storability because it is difficult to generate sulfurization.

By using the treatment liquid of the present invention, it is possible to prevent discoloration of the dye under low humidity even if it does not substantially contain formaldehyde, and the storage stability of the treatment liquid is excellent. It is possible to provide a color photographic processing solution which can improve the yellow stain in the unexposed area and improve the safety of the working environment.

Claims (4)

[Claims] 1. A color reversal image in which a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support is processed by black-and-white development and color development, and then at least a stabilizing solution. A method of processing a silver halide color photographic light-sensitive material, wherein the stabilizing solution contains a compound represented by the following general formula [F]. [Chemical 1] In the formula, Z represents an atomic group necessary for forming a carbocycle or a heterocycle, X represents an aldehyde group, and (In these groups, R ₁ and R ₂ each represent a lower alkyl group), and n represents an integer of 1 to 4. 2. The method of processing a silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic light-sensitive material contains a vinyl sulfonic acid type hardener. 3. A fixing solution or adjusting solution or a preliminary washing solution for silver halide color photographic light-sensitive materials, which contains a compound represented by the general formula [F]. [Chemical 3] In the formula, Z represents an atomic group necessary for forming a carbocycle or a heterocycle, X represents an aldehyde group, and (In these groups, R ₁ and R ₂ each represent a lower alkyl group), and n represents an integer of 1 to 4. 4. A silver halide color photograph characterized in that a silver halide color photographic light-sensitive material is treated with a fixing solution or an adjusting solution or a preliminary washing solution for a silver halide color photographic light-sensitive material according to claim 3. Method of processing photosensitive material.