JPH07134384A - Color image forming method - Google Patents

Abstract

PURPOSE:To provide a color image forming method by which color development time is shortened and color reproducibility and yellow stain due to bleach fog are improved. CONSTITUTION:A silver halide color photosensitive material contg. a yellow coupler represented by formula I in at least one silver halide emulsion layer on the base is color-developed in the presence of a p-phenylenediamine color developing agent represented by formula II or III to form a color image. In formula I, each of R<1> and R<3> is an alkyl, aryl or a hetero ring, R<2> is H, an alkyl, aryl or a hetero ring and X is a releasable group. In the formula II, R1 is, e.g. an alkyl, R2 is, e.g. an alkylene and R3 is an alkyl. In formula III, each of R4 and R5 is, e.g. >=2C hydroxyalkyl and R6 is an alkyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color image forming method, and more particularly to a color image forming method which shortens the processing time and provides excellent photographic properties and improved yellow stain.

[0002]

2. Description of the Related Art Generally, the basic steps of processing a silver halide color photographic light-sensitive material (hereinafter, also referred to as "light-sensitive material") include a color development step and a desilvering step. In the color developing step, the silver halide exposed by the color developing agent is reduced to produce silver, and the oxidized color developing agent reacts with the color developing agent (coupler) to give a dye image. In the next desilvering step, the silver generated in the color developing step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then,
It is dissolved by a complexing agent of silver ions, which is commonly called a fixing agent. Through this desilvering process, only the dye image is formed on the color light-sensitive material.

The above desilvering process is carried out in two baths of a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, and in one bath with a bleaching fixing agent in which a bleaching agent and a fixing agent are allowed to coexist. It may be done. The actual development processing includes various auxiliary steps such as maintaining physical quality or improving image storability. For example, a hardening bath, a stopping bath, an image stabilizing bath, a washing bath and the like. In recent years, with the spread of small in-store processing service systems called minilabs,
In order to promptly respond to a processing request from a customer and to reduce maintenance work of these processing machines, there has been a strong demand for a reduction in the time required for the above processing and a low replenishment.

Currently, 4- (N-ethyl-N) is widely used as a color developing agent in the processing of color negative films.
A method of shortening the processing time by using various color developing agents having high developing activity as compared with -β-hydroxyethylamino) -2-methylaniline is disclosed in JP-A-5-1971.
09, JP-A-5-188549 and the like. However, by the method as described in the patent, the processing time can be shortened to some extent, but the development of a layer (lower layer) close to the support becomes the rate-determining supply of the developing agent, and It is delayed as compared with the development of the distant layer (upper layer), and as a result, the color balance is largely lost and the color reproducibility is significantly deteriorated. Further, when rapid processing is performed using a highly active color developing agent as described in the above-mentioned patent, there arises a problem that color stain (yellow stain) occurs in an unexposed area.

The yellow stain generated after this processing is due to bleaching fog, and when the light-sensitive material is transferred from the color developing solution to the processing solution having the next bleaching agent, the color developing agent is brought in, and the color developing agent is changed by the bleaching agent. It occurs because it is oxidized and undergoes a coupling reaction with the yellow coupler. this is,
A high activity color developing agent is particularly large, and further, when the replenishing amount of the processing solution having a bleaching agent is reduced, the deterioration is further deteriorated, and improvement has been desired.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a color image forming method in which the color development time is shortened, the color reproducibility is improved, and especially the yellow stain due to bleaching fog is improved. Another object of the present invention is to provide a color image forming method which is excellent in color developability even when the color development time is shortened, and which further improves yellow stain due to bleaching fog and yellow stain when stored under high temperature and high humidity. To provide. Another object of the present invention is to provide a color image forming method which achieves the above object even when the replenishing amount of a processing solution having a bleaching ability is reduced.

[0007]

The above objects have been achieved by the following method. That is, a silver halide color photographic light-sensitive material containing at least one yellow coupler represented by the following general formula (1) in at least one silver halide emulsion layer provided on a support is prepared by the following general formula: It is achieved by a color image forming method characterized by performing color development in the presence of at least one p-phenylenediamine color developing agent represented by (D1) or (D2).

General formula (1) R ¹ OCOCH (X) CONR ² R ³

In the formula (1), R ¹ represents an alkyl group, an aryl group or a heterocyclic group, R ² represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ³ represents an alkyl group or an aryl group. Alternatively, it represents a heterocyclic group, and X represents a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Here, R ² and R ³ may combine with each other to form a ring.

[0010]

[Chemical 3]

In the formula (D1), R ₁ is a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight chain having 2 to 8 carbon atoms in the main chain and having 2 to 8 carbon atoms in total. Represents a chain or branched hydroxyalkyl group. R ₂ is a straight-chain or branched unsubstituted alkylene group having a main chain of 3 to 8 carbon atoms and having a total of 3 to 8 carbon atoms, or a total number of carbon atoms having a main chain of 3 to 8 carbon atoms is 3 Represents a linear or branched hydroxyalkylene group of -8. R ₃ represents a linear or branched alkyl group having 1 to 4 carbon atoms.

[0012]

[Chemical 4]

In the formula (D2), when R ₄ represents a hydroxyalkyl group having a total carbon number of 2 or more, R ₅ also represents a hydroxyalkyl group having a total carbon number of 2 or more, and R ₆ represents an alkyl group. Represent However, R ₄ and R ₅ may be the same or different, and the total number of carbon atoms of R ₄ , R ₅ and R ₆ is 10
It is the following. When R ₄ represents an unsubstituted alkyl group having 1 to 3 carbon atoms, R ₅ represents at least a hydroxy group.
R ₆ represents an alkyl group having 1 or more, and R ₆ represents an alkyl group having 1 to 4 carbon atoms.

Further, in the method of processing with a processing solution having a bleaching ability after the above-mentioned color development, when the replenishing amount of the processing solution is 45 ml to 500 ml per 1 m ^{2 of the} light-sensitive material, the effect of the present invention becomes particularly remarkable. appear. In the present invention, the replenishing amount of the processing solution having a bleaching agent is preferably 45 to 500 ml, more preferably 50 to 400, per 1 m ² of the light-sensitive material.
ml, particularly preferably 50 to 300 ml, most preferably 50 to 200 ml.

The yellow coupler represented by the general formula (1) used in the present invention will be described in detail below. Formula (1)
In, the alkyl group represented by R ¹ has 1 carbon atom.
To 36, preferably 1 to 24, which may be substituted. Examples of the alkyl group represented by R ¹ include a secondary alkyl group (having 3 to 36 carbon atoms, preferably 3 to 24 carbon atoms) and a tertiary alkyl group (having 4 to 36 carbon atoms, preferably 4 to 2 carbon atoms).
4) or a cycloalkyl group (having 3 to 36 carbon atoms, preferably 5 to 24 carbon atoms) is preferable because of excellent fastness of the color image of the coupler. Examples of alkyl groups include methyl,
Ethyl, n-butyl, n-dodecyl, 2-hexyldecyl, benzyl, phenethyl, 2-ethylhexyl, neopentyl, isopropyl, isobutyl, sec-butyl, 1-methyldodecyl, t-butyl, 1,1-dimethylpropyl, 2 -Ethyl-1,1-dimethylhexyl,
1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1-methyl-1- (4-methylcyclohexyl) ethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methyl-2,6-di-t
-Butylcyclohexyl, 2,6-dimethylcyclohexyl, 1-methylcyclohexyl, 1-adamantyl,
Bornyl, norbornyl, menthyl, fentyl, 2-
n-butyl fentyl etc. are mentioned.

In the formula (1), the alkyl group represented by R ² and R ³ has 1 to 36 carbon atoms, preferably 1 to 24 carbon atoms, and may be linear, branched or cyclic. It may be present or may be substituted. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, dodecyl, cyclohexyl, benzyl, phenethyl and the like.

In the formula (1), the aryl group represented by R ¹ , R ² and R ³ has 6 to 48, preferably 6 to 36 carbon atoms and may be substituted. As the aryl group, an aryl group having a substituent at the ortho position is preferable since the fastness of the color image of the coupler is excellent. An aryl group having a substituent at both ortho positions is more preferable.
Examples of aryl groups include phenyl, naphthyl and the like, which may be further substituted.

In the formula (1), the heterocyclic group represented by R ¹ , R ² and R ³ is preferably a 5- to 7-membered ring, the heteroatoms are preferably nitrogen, oxygen and sulfur atoms, and the carbon number is 1-48 are preferable, for example, 2-furyl, 2-thienyl, 2-pyridyl, 2-imidazolyl, 2- (1,
3-oxazolyl), 5-tetrazolyl, 1-piperidinyl, 5-indolinyl, 1,3,4-thiadiazole, benzoxazol-2-yl, benzothiazol-2-yl, benzimidazol-2-yl, 1,2,
4-triazol-5-yl, 3-pyrazolyl, 2-morpholyl, 4-morpholyl, 2-quinolyl, 2-quinazolyl and the like can be mentioned, which may be further substituted.

In the formula (1), X represents a group (leaving group) capable of leaving when the coupler compound reacts with an oxidized product of an aromatic primary amine developing agent. Preferred as X is an aryloxy group (eg, phenoxy, naphthoxy, etc.),
Heterocyclic oxy group, arylthio group, heterocyclic thio group,
Cyclic imide group (for example, 2,4-dioxo-1,3-imidazolidine-3-, which is bonded to the coupling position at a nitrogen atom)
2,4-dioxo-1,3-oxazolidine-3
-Yl, 3,5-dioxo-1,2,4-triazolidin-4-yl, succinimide, phthalimide, 1,3
-Imidazolidin-2,4,5-trion-1-yl,
2,4-dioxo-1,3-imidazolidin-1-yl, etc.), unsaturated nitrogen-containing heterocyclic groups (eg, 1-pyrrolyl, 1-imidazolyl, 1-pyrazolyl) which are bonded to the coupling position at a nitrogen atom. , 2,4-triazole-1
(Or 4) -yl, 1,2,3-triazol-1-
Yl, 1 (or 2) -tetrazolyl, benzotriazol-1-yl, 3-pyrazolin-5-one-1-yl, etc.), or a carbonyl group bonded to the coupling position at a nitrogen atom and in the ring. A heterocyclic group having (for example, imidazolin-2-one-1-yl, 2-pyridone-1
-Ill). More preferred as X is a heterocyclic group (including a cyclic imide group) that is bonded to the coupling position at a nitrogen atom, and particularly preferably a cyclic imide group or an azolyl group.

These leaving groups are non-photographic useful groups or photographically useful groups or their precursors (eg, development inhibitors,
Development accelerator, desilvering accelerator, fogging agent, dye, hardener,
Coupler, developing agent oxidant scavenger, fluorescent dye,
It may be either a developing agent or an electron transfer agent).
When X represents a photographically useful group, conventionally known examples are useful. For example, U.S. Pat. No. 4,24
8,962, 4,409,323, 4,43
8,193, 4,421,845, 4,61
8,571, 4,652,516, 4,86
1,701, 4,782,012, 4,85
7,440, 4,847,185, 4,47
7,563, 4,438,193, 4,62
8,024, 4,618,571, 4,74
No. 1,994, European Patent Publication No. 193,389A
Nos. 348,139A and 272,573A. Among the photographically useful groups, a development inhibitor, an electron transfer agent, a desilvering accelerator (bleaching accelerator) or a dye is preferable.

If R ¹ , R ² , R ³ and X described above are alkyl, aryl or heterocycles or contain groups thereof, they may have substituents, examples of substituents Include the following groups (hereinafter referred to as Substituent Group A). Halogen atom (for example, fluorine atom, chlorine atom), alkoxycarbonyl group (having 2 to 36 carbon atoms, preferably 2 to 24. For example, methoxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl),
Acylamino group (having 2 to 36 carbon atoms, preferably 2 to 2 carbon atoms)
4. For example, acetamide, tetradecanamide, 2-
(2,4-di-t-amylphenoxy) butanamide,
Benzamide), sulfonamide group (C1-C36,
Preferably 1-24. For example, methanesulfonamide, dodecanesulfonamide, hexadecanesulfonamide,
Benzenesulfonamide), carbamoyl group (C1
~ 36, preferably 1-24. For example, N-butylcarbamoyl, N, N-diethylcarbamoyl, N-mesylcarbamoyl), sulfamoyl group (having 0 to 36 carbon atoms, preferably 0 to 24 carbon atoms, such as N-butylsulfamoyl,
N-dodecylsulfamoyl, N-hexadecylsulfamoyl, N-3- (2,4-di-t-amylphenoxy) butylsulfamoyl, N, N-diethylsulfamoyl), alkoxy group (carbon Number 1 to 36, preferably 1 to 24. For example, methoxy, hexadecyloxy, isopropoxy), an aryloxy group (having 6 to 36 carbon atoms, preferably 6 to 24 carbon atoms, such as phenoxy, 4-methoxyphenoxy, 3-t-. Butyl-4-hydroxyphenoxy, naphthoxy), aryloxycarbonyl group (C7-36, preferably 7-24. For example, phenoxycarbonyl), N-acylsulfamoyl group (C2-C2).
36, preferably 2-24. For example, N-propanoylsulfamoyl, N-tetradecanoylsulfamoyl,
N-benzoylsulfamoyl), a sulfonyl group (having 1 to 36 carbon atoms, preferably 1 to 24. For example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, dodecanesulfonyl), a dialkylamino group (having 2 to 3 carbon atoms).
6. For example, dimethylamino, morpholino), alkoxycarbonylamino group (having 1 to 36 carbon atoms, preferably 1
~ 24. For example, ethoxycarbonylamino, tetradecyloxycarbonylamino), cyano group, nitro group, carboxyl group, hydroxyl group, sulfo group, alkylthio group (having 1 to 36 carbon atoms, preferably 1 to 24 carbon atoms, for example, methylthio, dodecylthio, dodecylcarbamoylmethylthio). ), An ureido group (having 1 to 36 carbon atoms, preferably 1 to 36 carbon atoms).
24. For example, N-phenylureido, N-hexadecylureido), an aryl group (having 6 to 36 carbon atoms, preferably 6 to 24. For example, phenyl, naphthyl, 4-methoxyphenyl), a heterocyclic group (having 1 to 36 carbon atoms, preferably) Is 1
~ 24. A monocyclic or condensed ring having 3 to 12, preferably a 5- or 6-membered ring containing at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. For example, 2-pyridyl, 4-pyridyl, 4-pyrimidinyl,
3-pyrazolyl, 1-pyrrolyl, 2,4-dioxo-
1,3-imidazolidin-1-yl, morpholino, indolyl), alkyl group (C1-C36, preferably 1)
~ 24 straight, branched, cyclic, saturated, unsaturated. For example, methyl, ethyl, isopropyl, cyclopropyl, t-pentyl, t-octyl, cyclopentyl, t-butyl,
s-Butyl, dodecyl, 2-hexyldecyl), an acyl group (having 1 to 36 carbon atoms, preferably 2 to 24. For example, acetyl, benzoyl), an arylthio group (having 6 to 3 carbon atoms).
6, preferably 6-24. For example, phenylthio, naphthylthio), sulfamoylamino group (having 0 to 36 carbon atoms,
Preferably 0 to 24. For example, N-butylsulfamoylamino, N-dodecylsulfamoylamino, N-phenylsulfamoylamino) or N-sulfonylsulfamoyl group (C1-C36, preferably 1-24).
Examples thereof include N-mesylsulfamoyl, N-ethanesulfonylsulfamoyl, N-dodecanesulfonylsulfamoyl, and N-hexadecanesulfonylsulfamoyl. The above substituents may further have a substituent. Examples of the substituent include the substituents mentioned here.

The coupler represented by the formula (1) has X,
In the groups represented by R ¹ , R ² and R ³ , a dimer or higher multimer (for example, telomer or polymer) which is bonded to each other through a divalent or higher group may be formed. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

Next, the preferred range of the compound of the present invention represented by the formula (1) will be described. The compound of the present invention represented by the formula (1) is preferably represented by the following general formula (2).

[0024]

[Chemical 5]

In the formula (2), R ¹ and X are the formula (1).
R ¹ and X are the same as each other, and R ⁴ is a hydrogen atom, a halogen atom, or a carbon atom number of 1 to 36 (preferably 1
To 24) alkoxy group, C6 to C36 (preferably 6 to 24) aryloxy group, C1 to C3
6 (preferably 1 to 24) alkyl group, 2 carbon atoms
To 36 (preferably 2 to 24) alkoxycarbonyl groups or 2 to 16 carbon atoms (preferably 2 to 12)
Represents a dialkylamino group, R ⁵ represents the substituent group A, and m represents an integer of 0 to 3. When m is plural, R ⁵ may be the same or different.

A preferred partial structure in the formula (2) is shown below. In the formula (2), R ¹ is a secondary alkyl group, a tertiary alkyl group, a cycloalkyl group, or an aryl group having at least one substituent at the ortho position. In the formula (2), R ⁴ is a halogen atom, an alkyl group, an alkoxy group, or an aryloxy group. Formula (2)
In, R ⁵ is a halogen atom, a cyano group, an alkoxycarbonyl group, an alkoxy group, a carbonamido group, a sulfonamide group, a carbamoyl group, or a sulfamoyl group. In Formula (2), m is an integer of 0-2. In the formula (2), X is a cyclic imide group (for example, imidazolidin-2,4-dione-3-yl, oxazolidin-2,4-dione-3-yl, thiazolidine-2,
4-dione-3-yl, triazolidine-3,5-dione-4-yl, imidazolidin-2,4,5-trion-1-yl, succinimide, glutarimide, diglycolimide, phthalimide) or azolyl group ( For example, 1-picolyl, 1-pyrazolyl, imidazolyl,
1,2,4-triazol-1-yl, 1,2,4-triazol-4-yl, 1,2,3-triazol-1
-Yl, 1-tetrazolyl, 2-tetrazolyl, 1-benzotriazolyl, 2-benzotriazolyl).
Specific examples of the coupler represented by the formula (1) are shown below.
The present invention is not limited to these.

[0027]

[Chemical 6]

[0028]

[Chemical 7]

[0029]

[Chemical 8]

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical 12]

[0034]

[Chemical 13]

[0035]

[Chemical 14]

[0036]

[Chemical 15]

[0037]

[Chemical 16]

[0038]

[Chemical 17]

[0039]

[Chemical 18]

[0040]

[Chemical 19]

[0041]

[Chemical 20]

[0042]

[Chemical 21]

[0043]

[Chemical formula 22]

These compounds are obtained by reacting a compound represented by the general formula (3) or the general formula (4) with XH (where X represents the same meaning as X in the general formula (1)) in the presence of a base. It can be easily synthesized by a method such as. General formula (3) R ¹ OCOCH (Br) CONR ² R ³ General formula (4) R ¹ OCOCH (Cl) CONR ² R ³ Synthesis examples of typical compounds of the present invention are shown below. Other compounds can be synthesized in the same manner as in the examples below.

Synthesis Example 1. Synthesis of Exemplified Compound (1) The compound was synthesized by the following synthetic route.

[0046]

[Chemical formula 23]

20.0 g of compound (A-1) and 8.42 g of compound (A-2) were mixed with 100 ml of N, N-dimethylacetamide and stirred at room temperature. 11.1 g of triethylamine was added dropwise over 20 minutes, and the mixture was further stirred for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate.
The organic layer was washed with water, a 5% aqueous sodium carbonate solution, and then diluted hydrochloric acid, and dried over magnesium sulfate. The desiccant was filtered off and the solvent was distilled off to give a yellow oil. Purification by silica gel chromatography gave 16.0 g of the target exemplary compound (1) as a pale yellow oily substance.

Synthesis Example 2. Synthesis of Exemplified Compound (4) It was synthesized by the following synthetic route.

[0049]

[Chemical formula 24]

25.0 g of compound (A-3) and 8.21 g of compound (A-4) were mixed with 150 ml of N, N-dimethylacetamide and stirred at room temperature. Triethylamine 9.65 g was added dropwise over 15 minutes, and the mixture was further stirred for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate.
The organic layer was washed with water, a 5% aqueous sodium carbonate solution, and then diluted hydrochloric acid, and dried over magnesium sulfate. The desiccant was filtered off and the solvent was distilled off to give a yellow oil. Purification by silica gel chromatography gave 21.8 g of the desired exemplary compound (4) as a colorless oil.

Synthesis Example 3. Synthesis of Exemplified Compound (9) It was synthesized by the following synthetic route.

[0052]

[Chemical 25]

20.0 g of compound (A-5) and 16.5 g of compound (A-6) were mixed with 100 ml of N, N-dimethylacetamide and stirred at room temperature. 9.35 g of triethylamine was added dropwise over 20 minutes, and the mixture was further stirred for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate.
The organic layer was washed with water, a 5% aqueous sodium carbonate solution, and then diluted hydrochloric acid, and dried over magnesium sulfate. The desiccant was filtered off and the solvent was distilled off to give a yellow oil. Purification by silica gel chromatography gave 19.3 g of the desired exemplary compound (9) as a colorless glassy solid.

Synthesis Example 4. Synthesis of Exemplified Compound (20) It was synthesized by the following synthetic route.

[0055]

[Chemical formula 26]

50.0 g of compound (A-7) and 38.1 g of compound (A-8) were mixed with 300 ml of N, N-dimethylacetamide and stirred at room temperature. Triethylamine 17.6 g was added dropwise over 30 minutes, and the mixture was further stirred for 2 hours. The reaction mixture was poured into water and extracted with ethyl acetate.
The organic layer was washed with water, a 5% aqueous sodium carbonate solution, and then diluted hydrochloric acid, and dried over magnesium sulfate. The desiccant was filtered off and the solvent was distilled off to give a yellow oil. Purification by silica gel chromatography gave 53.3 g of the desired exemplary compound (20) as a pale yellow oil.

Synthesis Example 5. Synthesis of Exemplified Compound (21) It was synthesized by the following synthetic route.

[0058]

[Chemical 27]

25.0 g of compound (A-9) and 13.7 g of compound (A-8) were mixed with 150 ml of N, N-dimethylacetamide and stirred at room temperature. 6.33 g of triethylamine was added dropwise over 15 minutes, and the mixture was further stirred for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate.
The organic layer was washed with water, a 5% aqueous sodium carbonate solution, and then diluted hydrochloric acid, and dried over magnesium sulfate. The desiccant was filtered off and the solvent was distilled off to give a yellow oil. Purification by silica gel chromatography gave 22.5 g of the desired exemplary compound (21) as a colorless glassy solid.

Synthesis Example 6. Synthesis of Exemplified Compound (27) It was synthesized by the following synthetic route.

[0061]

[Chemical 28]

30.0 g of compound (A-10) and 22.1 g of compound (A-11) were mixed with 200 ml of N, N-dimethylacetamide and stirred at room temperature. Triethylamine (10.3 g) was added dropwise over 40 minutes, and the mixture was further stirred for 3 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water, a 5% aqueous sodium carbonate solution, and then diluted hydrochloric acid, and dried over magnesium sulfate. The desiccant was filtered off and the solvent was distilled off to give a yellow oil. Purification by silica gel chromatography gave 32.1 g of the desired exemplary compound (27) as a pale yellow glassy solid.

The yellow coupler represented by formula (1) of the present invention is preferably added to the light-sensitive silver halide emulsion layer in the light-sensitive material or its adjacent layer, and is added to the light-sensitive silver halide emulsion layer. Is particularly preferred. When the leaving group X contains a component of a photographically useful group, the total addition amount thereof is 0.0001 to 0.80 g / m ² , and preferably 0.0005 to 0.50 g. / M ² , more preferably 0.02 to 0.30 g / m ² . Further, when the leaving group X does not contain a component of a photographically useful group, the addition amount thereof is 0.001 to 1.20 g / m ² , preferably 0.01 to 1.00 g / m ^2. , And more preferably 0.
It is 10 to 0.80 g / m ² . The coupler of the present invention can be added to a light-sensitive material in the same manner as an ordinary coupler as described later.

The general formula (D1) will be described in detail below. In the general formula (D1), R ₁ is a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight-chain having 2 to 8 carbon atoms in which the main chain has 2 to 8 carbon atoms, or Represents a branched hydroxyalkyl group. Here, the main chain refers to a connecting chain of a nitrogen atom and a hydroxyl group to be connected, and when R ₁ has a plurality of hydroxyl groups, it means one having the smallest number of carbon atoms. Specific examples of R ₁ include, for example, methyl, ethyl, n-propyl,
Isopropyl, n-butyl, sec-butyl, n-hexyl, neopentel, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 4-hydroxypentyl, 3-hydroxybutyl , 4-hydroxy-4
-Methylpentyl, 5,6-dihydroxyhexyl, 7
-Hydroxyheptyl, 6-hydroxyoctyl, 8-
Hydroxyoctyl etc. are mentioned.

R ₂ is a straight-chain or branched unsubstituted alkylene group having a main chain of 3 to 8 carbon atoms and a total of 3 to 8 carbon atoms, or a main chain of 3 to 8 carbon atoms. The sum is 3
Represents a linear or branched hydroxyalkylene group of -8. Here, the main chain means the nitrogen atom connecting the main chain and the general formula (D
1) Refers to a linking chain of the hydroxyl group described in 1), and when R ₂ has one or more hydroxyl groups, it is bonded to the carbon atom having the smallest carbon number counted from the nitrogen atom side. The hydroxyl group having the general formula (D
It corresponds to the hydroxyl group described in 1), and its connecting chain is the main chain. Specific examples of R ₂ include trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, 3-methylpentamethylene, 2-methylpentamethylene, 2-ethyltrimethylene, 3- (2-hydroxyethyl) trimethylene, 6- (1,2-dihydroxyethyl) hexamethylene and the like can be mentioned.

In the general formula (D1), R ₁ and R
₂ is a linear or branched unsubstituted alkyl group R ₁ from 1 to 4 carbon atoms, R ₂ is the main chain is a linear or branched unsubstituted alkylene group having 4 to 6 carbon atoms Or the total number of carbon atoms of the main chain of R ₁ is 3 to 8 is 3 to 8
A linear or branched hydroxyalkyl group of
The main chain of R ₂ is preferably a straight-chain or branched unsubstituted alkylene group having 3 to 8 carbon atoms, particularly 3 to 6 carbon atoms.
More preferably, in the general formula (D1), R ₁ is a linear or branched unsubstituted alkyl group having 1 to 4 carbon atoms and R ₂ is a tetramethylene group.

In the general formula (D1), R ₁ has ₁ carbon atom
When it is a straight-chain or branched unsubstituted alkyl group of -4, the carbon number thereof is more preferably 1-3. Of these, a methyl group and an ethyl group are particularly preferable, and an ethyl group is most preferable.

R ₃ is a linear or branched alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, and most preferably a methyl group.

Specific examples of typical developing agents represented by formula (D1) in the invention are shown below, but the invention is not limited to these.

[0070]

[Chemical 29]

[0071]

[Chemical 30]

The color developing agent represented by formula (D1) of the present invention is, for example, Journal of the American
Chemical Society Volume 73, page 3100 (1951), British Patent No. 807,899, European Patent Publication No. 517214.
It can be easily synthesized according to the method described in A1 and JP-A-3-246543 and JP-A-4-443. Among the compounds represented by formula (D1). Exemplified compound D-12 may be mentioned as the most preferable compound.

The compound represented by the general formula (D1) may be stored as a free amine, but in general, it is prepared and stored as a salt of an inorganic acid or an organic acid, and is not converted to the free amine until it is added to the treatment liquid. It is preferable to do so. Examples of the inorganic or organic acid that forms a salt of the compound of the general formula (D1) include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, naphthalene-1,5-disulfonic acid and the like. Of these, salts of sulfuric acid and p-toluenesulfonic acid are preferable, and salts of sulfuric acid are most preferable. For example, exemplary compound D-12
Is obtained as a sulfate, the melting point of which is 112 to 114 ° C.
(Recrystallized from water-ethanol), and Exemplified Compound D-2 was also obtained as a sulfate, the melting point of which was 158 to 16
0 ° C. (recrystallized from water-ethanol).

In the present invention, R ₄ , R ₅ and R ₆ of the compound represented by the general formula (D2) will be described in detail below. When R ₄ is a hydroxyalkyl group having a total carbon number of 2 or more, R ₅ is also a hydroxyalkyl group having a total carbon number of 2 or more, and R ₄ and R ₅ may be the same or different. More specifically, R ₄ and R ₅ have a total carbon number of 2 to
7 is a linear, branched or cyclic hydroxyalkyl group, and the hydroxy group may be primary, secondary or tertiary, and the hydroxy group may be one or two or more. Well, for example, 2-hydroxyethyl, 3-hydroxypropyl, 3-hydroxycyclopentyl, 2-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 2,3-dihydroxypropyl, 6-hydroxyhexyl, 4-hydroxypentyl, 3-hydroxybutyl, 4-hydroxy-4-methylpentyl,
5,6-dihydroxyhexyl, 7-hydroxyheptyl, 4-hydroxycyclohexyl, 3,4-dihydroxybutyl, 3-hydroxy-2- (hydroxymethyl) propyl, 2,3,4-trihydroxybutyl, 4
-Hydroxy-3- (hydroxymethyl) butyl, 2-
It is hydroxy-2-methylpropyl. R ₄ and R ₅ are preferably linear or branched hydroxyalkyl groups. At least one of R ₄ and R ₅ is preferably a hydroxyalkyl group, which is a primary hydroxy group. The total number of hydroxy groups contained in R ₄ and R ₅ is preferably 4 or less, more preferably 3 or less, and most preferably 2.

R ₆ is an alkyl group having 1 to ₆ carbon atoms.
More specifically, R ₆ is a linear, branched or cyclic alkyl group having 1 to ₆ carbon atoms, such as methyl, ethyl or n-.
Propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-hexyl, neopentyl and cyclopropyl. The total number of carbon atoms possessed by R ₄ , R ₅ and R ₆ is 10 or less. The total number of carbon atoms is preferably 6 to 10, more preferably R ₆ is a methyl group, an ethyl group, an isopropyl group or a t-butyl group and the total number of carbon atoms is 6 to 10. Most preferably, it is 7-9.

[0076] Next, described below in detail for R _4, R ₅ and R ₆ when R ₄ is an unsubstituted alkyl group having 1 to 3 carbon atoms. R ₄ is an alkyl group having 1 to 3 carbon atoms, and more specifically, R ₄ is methyl, ethyl, n-propyl, is
It is o-propyl. R ₅ is an alkyl group having at least two hydroxy groups. More specifically, R ₅
Has 3 to more carbon atoms and at least 2 hydroxy groups
10, preferably 3 to 7 linear, branched or cyclic alkyl groups, which may be primary, secondary or tertiary, such as 3,4-dihydroxybutyl, 4 , 5-dihydroxypentyl, 2,3-dihydroxypropyl, 2,4-dihydroxybutyl, 5,6
-Dihydroxyhexyl, 6,7-dihydroxyheptyl, 3,4-dihydroxycyclohexyl, 3-hydroxy-2- (hydroxymethyl) propyl, 2,3,4
-Trihydroxybutyl, 3,4,5-trihydroxypentyl, 4-hydroxy-3- (hydroxymethyl)
Butyl, 2,3-dihydroxy-2-methylpropyl,
3,4-dihydroxy-2-methylbutyl, 2,3
4,5,6-Pentahydroxyhexyl, 3,4,5-
Trihydroxypentyl, 2,3,4,5-tetrahydroxypentyl and 2,3-dihydroxybutyl.
R ₅ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. R
_The number of hydroxy groups carried by ₅ is preferably 3 or less, and more preferably 2.

R ₆ is an alkyl group having 1 to 4 carbon atoms,
More specifically, R ₆ is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl. In the general formula (D2), the total carbon number of R ₄ , R ₅ and R ₆ is preferably 5-10, and 5-9
More preferably, R ₆ is a methyl group or an ethyl group, and the total number of carbon atoms is more preferably 5-9, and most preferably 6-7. Specific examples of typical developing agents represented by formula (D2) in the invention are shown below, but the invention is not limited thereto.

[0078]

[Chemical 31]

[0079]

[Chemical 32]

[0080]

[Chemical 33]

[0081]

[Chemical 34]

[0082]

[Chemical 35]

Since the compound represented by the general formula (D2) is extremely unstable when stored as a free amine, it is generally produced and stored as a salt of an inorganic acid or an organic acid,
It is preferable that the free amine is not added until it is added to the treatment liquid. Examples of the inorganic or organic acid which forms the salt of the compound of the general formula (D2) include hydrochloric acid, sulfuric acid, phosphoric acid, p
-Toluenesulfonic acid, methanesulfonic acid, naphthalene-1,5-disulfonic acid and the like can be mentioned. Of these, salts of sulfuric acid and p-toluenesulfonic acid are preferable, and salts of sulfuric acid are most preferable. The color developing agent represented by the general formula (D2) of the present invention is, for example, the method described in Journal of the American Chemical Society, Volume 73, page 3100 (1951), British Patent No. 807,899. Can be easily synthesized. Further, the following synthesis examples and methods similar thereto can also be used. Synthesis Example An exemplary compound (D-31) of the present invention was synthesized according to the following formula.

[0084]

[Chemical 36]

Synthesis of (1-a) 20 g of m-anisidine and 34.2 g of sodium hydrogen carbonate
And 9.7 g of sodium iodide, 80 g of dimethylacetamide
3-chloro-1 while stirring at 120 ° C.
-Propanol 38.4g was added over 1 hour, and it heat-stirred for further 4 hours. After cooling, the system was poured into water, extracted with ethyl acetate, washed with water, concentrated and purified by silica gel column chromatography to obtain 35 g of (1-a) as a yellow oil.

Synthesis of (1-b) 43.4 g of (1-a), 200 ml of water and 33.
The mixture was added to 3 g of the mixed solution, and at an internal temperature of 5 ° C, a solution of sodium nitrite 11.9 g in water 50 ml was added over 30 minutes.
The mixture was further stirred for 1 hour at room temperature. Sodium bicarbonate 1
After 8.3 g was added, the reaction mixture was concentrated, the inorganic matter was filtered, and then purified by silica gel column chromatography to obtain (1-b) 40 g as a green oily substance.

Synthesis of Exemplified Compound (D-31) 40 g of (1-b) and 0.5 g of 10% palladium-carbon were added to 200 ml of methanol, and hydrogen pressure was 50 kg / cm ² in an autoclave at an internal temperature of 40 ° C. Stir for hours.
After the catalyst was filtered off, the filtrate was added dropwise to a methanol solution of 53.7 g of 1,5-naphthalenedisulfonic acid tetrahydrate. The precipitated crystals were collected by filtration to give 1,5-naphthalenedisulfonic acid salt of the target exemplary compound (D-31) as colorless crystals.
Obtained 5.5 g. Melting point 262 [deg.] C (decomposition). Elemental analysis value (%) as C ₂₃ H ₃₀ N ₂ O ₉ S ₂ C H N S calculated value: 50.86 5.53 5.16 11.79 measured value: 50.60 5.55 5.01 11 .63

The amount of the color developing agent represented by the general formula (D1) or (D2) of the present invention is preferably 0.3 mmol to 100 mmol, more preferably 3 mmol to 90, per liter of the color developing solution. Concentrations of millimolar, particularly preferred 15 millimolar to 50 millimolar.

The color developing agents of the present invention may be used alone or in combination of two or more, and may be used in combination with other known p-phenylenediamine derivatives. Representative examples of the compound to be combined are shown below, but the invention is not limited thereto. P-1 N, N-diethyl-p-phenylenediamine P-2 2-amino-5- (N, N-diethylamino)
Toluene P-3 2-amino-5- (N-ethyl-N-laurylamino) toluene P-4 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline P-5 2-methyl-4 -[N-Ethyl-N- (β-hydroxyethyl) amino] aniline P-6 4-amino-3-methyl-N-ethyl-N-
[Β- (Methanesulfonamide) ethyl] aniline P-7 N- (2-amino-5-N, N-diethylaminophenylmethyl) methanesulfonamide P-8 N, N-dimethyl-p-phenylenediamine P-9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline P-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline P-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline

Of the above-mentioned p-phenylenediamine derivatives, the exemplified compound P is particularly preferable as the compound to be combined.
-5 or P-6. In addition, these p-phenylenediamine derivatives and sulfates, hydrochlorides, sulfites, p-
Toluenesulfonate, nitrate, naphthalene-1,5-
It is generally used in a salt such as a disulfonate. The total amount of the aromatic primary amine developing agent used is preferably about 0.3 mmol to about 70 per liter of the developing solution.
Mmol, more preferably 10 to 60 mmol, most preferably 15 to 50 mmol. When used in combination, the amount of the developing agent is such that the amount represented by the general formula (D1) or (D2) of the present invention does not impair the effects of the present invention.
It is preferable to use 1/10 to 10 mol per 1 mol of the developing agent. The color developer used in the present invention is generally alkaline, and preferably has a pH of 9 to 1.
It is an alkaline aqueous solution of 2.5.

In the color developing solution of the present invention, compounds which directly preserve the aromatic primary amine color developing agent are disclosed in JP-A-63-5341, JP-A-63-106655 and JP-A-4-144445. Various hydroxylamines, hydroxamic acids described in JP-A-63-43138, hydrazines and hydrazides described in JP-A-63-146041, and phenols described in JP-A-63-44657 and 63-58443. Type 63-
[Alpha] -hydroxyketones and [alpha] -aminoketones described in No. 44658, various sugars described in No. 63-36244, and the like can be contained. In addition, in combination with the above compound, JP-A-63-4235, JP-A-63-24254,
No. 63-21647, No. 63-146040, No. 6
3-27841 and 63-25654, etc., monoamines, 63-30845, 63-14.
640, 63-43169 and the like diamines, 63-21647, 63-26655 and 63-46655, and polyamines 63.
No. 53551, Nitroxy Radicals, 63
The alcohols described in -43140 and 63-53549, the oximes described in 63-56654, and the tertiary amines described in 63-239447 can be used. Other preservatives include JP-A-57
Nos. 44148 and 57-53749, various metals, 59-180588, salicylic acids, 54-3582, alkanolamines, and 56-94349, polyethyleneimines. If desired, the aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be contained.
Especially when hydroxylamines are used, it is preferable to use the above-mentioned alkanolamines and aromatic polyhydroxy compounds in combination. As a particularly preferred preservative, JP-A-3
Hydroxylamines represented by the general formula (I) of No. 144446, and among them, compounds having a methyl group, an ethyl group, a sulfo group or a carboxy group are preferable. The addition amount of these preservatives is 20 mmol to 200 mmol, preferably 30 mmol to 150 mmol, per liter of color developing solution.

Others Various additives described in JP-A-3-144446 can be used in the color developing solution of the present invention. For example, carbonic acid, phosphoric acid, boric acid, hydroxybenzoic acid, etc. of the same patent page (9) can be used as a buffering agent for maintaining pH. It is preferable that the pH of the color developer is maintained at 9.0 to 12.5 by using these buffers. More preferably, it is 9.5 to 11.5. Examples of the antifoggants include halide ions and organic antifoggants described on page (10). In particular, when the concentration of the developing agent in the color developing solution is as high as 20 mmol / liter or higher and when the processing is performed at a high temperature of 40 ° C. or higher, the bromide ion concentration is preferably higher to some extent.
It is preferably 7 mmol / liter or more and 60 mmol or less. If necessary, the halogen can be removed by using an ion exchange resin or an ion exchange membrane to control the concentration within a preferable range. As the chelating agent, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid are preferably used. For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N,
N-trimethylenephosphonic acid, ethylenediamine-N,
Compounds typified by N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof are preferred. Furthermore, development inhibitors such as benzimidazoles, benzothiazoles or mercapto compounds, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
A viscosity-imparting agent or various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added if necessary.

The replenishing amount of the color developing solution of the present invention is preferably 650 ml or less per 1 m ^{2 in} the case of a light-sensitive material for photographing.
It is more preferably 0 ml or less, most preferably 350 ml or less. The lower limit is most preferably 80 ml or more. The bromide ion concentration in the replenisher can be reduced to 300 ml or less by reducing or not containing it. The processing temperature of the color developing solution is preferably 38 ° C. or higher, more preferably 40 ° C. or higher and 50 ° C. or lower. The processing time of the color developer is preferably 3 minutes 15 seconds or less and 20 seconds or more, and 2 minutes 3
It is more preferably 0 seconds or less and 30 seconds or more. Further, it is preferable to prevent evaporation of liquid and oxidation of air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio (cm ⁻¹ ) is preferably 0.05 or less, It is preferably 0.0005 to 0.01.
As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033,
The slit development processing method described in JP-A-63-216050 can be mentioned. Reducing the aperture ratio can be applied not only in both the color development step and the black and white development step, but also in the subsequent steps such as bleaching, bleach-fixing, fixing, washing and stabilizing. The developer can be regenerated and used. Regeneration of the developing solution means that the used developing solution is subjected to anion exchange resin or electrodialysis, or the processing solution called a regenerant is added to increase the activity of the developing solution and to use it again as a processing solution. . In this case, the regeneration rate (ratio of the overflow solution in the replenisher) is preferably 50% or more, particularly preferably 70% or more. As a regeneration method, it is preferable to use an anion exchange resin. Regarding the particularly preferable composition of the anion exchange resin and the method for regenerating the resin, DIAION MANUAL (I) issued by Mitsubishi Kasei Kogyo Co., Ltd.
4th edition). Further, among the anion exchange resins, JP-A-2-952 and JP-A-1
Resins having compositions described in No. 281152 are preferred.

In the present invention, the color-developed light-sensitive material is desilvered. The desilvering process here basically comprises a bleaching process and a fixing process, but it is constituted by combining a bleach-fixing process in which these processes are performed simultaneously and these processes.

Examples of the bleaching agent of the present invention include inorganic compounds such as red blood salt, ferric chloride, dichromate, persulfate and bromate, and aminopolycarboxylic acid ferric complex salt, aminopolyphosphonic acid. Some organic compounds of ferric complex salts can be mentioned. In the present invention, it is preferable to use ferric aminopolycarboxylic acid complex salts from the viewpoints of environmental protection, handling safety, metal corrosiveness, and the like.

Specific examples of the ferric aminopolycarboxylic acid complex salt in the present invention are shown below, but the invention is not limited thereto. The redox potential is also shown. No. Compound redox potential (mV vs. NHE, pH = 6) 1. N- (2-acetamido) iminodiacetic acid ferric iron complex salt 180 2. Methyliminodiacetic acid ferric complex 200 3. Iminodiacetic acid ferric iron complex salt 210 4.1,4-butylenediaminetetraacetic acid ferric iron complex salt 230 5. Diethylene thioether diamine tetraacetic acid ferric iron complex salt 230 6. Glycol ether diamine tetraacetic acid ferric iron complex salt 240 7.1,3-Propylene diamine tetraacetic acid ferric iron complex salt 250 8. Ferric ethylenediamine tetraacetic acid complex salt 110 9. Diethylenetriamine pentaacetic acid ferric iron complex salt 80 10. Trans-1,2-cyclohexanediaminetetraacetic acid ferric complex salt 80

The redox potential of the bleaching agent is measured by the method described in Transactions of the Faraday Society, Volume 55 (1959), pp. 1312 to 1313. It is defined by the redox potential obtained by In the present invention, a bleaching agent having an oxidation-reduction potential of 150 mV or more is preferable, a bleaching agent having an oxidation-reduction potential of 180 mV or more, and most preferably 200 mV or more is preferable from the viewpoint of rapid processing and the effect of the present invention. is there. If the redox potential is too high, bleaching fog will occur, so the upper limit is 700 mV or less, preferably 500.
It is mV or less. Among these, particularly preferred is compound No. 7, 1,3-propylenediaminetetraacetic acid ferric complex.

The ferric aminopolycarboxylic acid complex salt is used as a salt of sodium, potassium, ammonium or the like.
Ammonium salts are preferred because of the fastest bleaching. The amount of the bleaching agent used in the bleaching solution is preferably 0.01 to 0.7 moles per liter of the bleaching solution, and is 0.25 to 0.7 moles for speeding up the treatment and reducing stain over time. preferable.
Particularly preferred is 0.30 to 0.6 mol. The amount of the bleaching agent used in the bleach-fixing solution is 0.01 to 0.5 mol, preferably 0.02 to 1 mol, per liter of the bleach-fixing solution.
It is 0.2 mol. Further, in the present invention, the oxidizing agents may be used alone or in combination of two or more kinds, and when two or more kinds are used in combination, the total concentration may be within the above range.

When the ferric aminopolycarboxylic acid complex salt is used in the bleaching solution, it can be added in the form of the complex salt as described above. However, the complexing compound aminopolycarboxylic acid and the ferric salt are used. (For example, ferric sulfate, ferric chloride,
Ferric nitrate, ferric ammonium sulfate, and ferric phosphate) may coexist to form a complex salt in the treatment liquid. In the case of this complex formation, the aminopolycarboxylic acid may be added in a slight excess over the amount required for complex formation with ferric ion, and when added excessively, it is usually 0.01 to 1
It is preferable to make it excessive in the range of 0%.

The bleaching solution as described above generally has a pH of from 2 to.
Used in 7.0. In order to accelerate the processing, the bleaching solution preferably has a pH of 2.5 to 5.0, more preferably 3.0 to 4.8, and particularly preferably 3.5 to 4.5.
It is preferable that the replenisher is used as 2.0 to 4.2. In the present invention, a known acid can be used to adjust the pH to the above range. As such an acid, an acid having a pKa of 2 to 5.5 is preferable. In the present invention, pKa represents the logarithmic value of the reciprocal of the acid dissociation constant, and shows the value determined at 25 ° C. at an ionic strength of 0.1 mol / dm. It is preferable to add 0.5 mol / liter or more of an acid having a pKa in the range of 2.0 to 5.5 to the bleaching solution because it is possible to prevent bleaching fog and precipitation of the replenisher due to low temperature aging. This pKa 2.0 to 5.5
Examples of the acid include inorganic acids such as phosphoric acid, acetic acid, malonic acid,
Although any organic acid such as citric acid may be used, the acid having a pKa of 2.0 to 5.5, which effectively exhibits the effect by the above improvement, is an organic acid. Further, among the organic acids, organic acids having a carboxyl group are particularly preferable. pKa is from 2.0
The organic acid of 5.5 may be a monobasic acid or a polybasic acid. In the case of a polybasic acid, its pKa is 2.
If it is in the range of 0 to 5.5, it can be used as a metal salt (for example, sodium or potassium salt) or an ammonium salt. Also, two or more kinds of organic acids having pKa of 2.0 to 5.5 can be mixed and used. However, the acid mentioned here excludes aminopolycarboxylic acids, salts thereof and Fe complex salts thereof.

PKa2. That can be used in the present invention.
Preferable specific examples of the organic acid of 0 to 5.5 include acetic acid, monochloroacetic acid, monobromoacetic acid, glycolic acid,
Aliphatic monobasic acids such as propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, acrylic acid, butyric acid, isobutyric acid, pivalic acid, aminobutyric acid, valeric acid, isovaleric acid; asparagine, alanine, arginine, ethionine, Glycine, glutamine, cystine, serine, methionine,
Amino acid compounds such as leucine; benzoic acid and mono-substituted benzoic acids such as chloro and hydroxy; aromatic monobasic acids such as nicotinic acid; oxalic acid, malonic acid, succinic acid,
Aliphatic dibasic acids such as tartaric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid, adipic acid;
Amino acid-based dibasic acids such as aspartic acid, glutamic acid and cystine; aromatic dibasic acids such as phthalic acid and terephthalic acid; and various organic acids such as polybasic acids such as citric acid. Among these, monobasic acids having a hydroxyl group and a carboxyl group are preferable, and glycolic acid and lactic acid are particularly preferable. The amount of glycolic acid and lactic acid used is 0.2 to 2 mol, preferably 0.5 to 1.5 mol, per liter of the bleaching solution. These acids are preferable because they exert the effects of the present invention more remarkably and suppress bleaching fog without odor. Further, the combined use of acetic acid and glycolic acid or lactic acid is preferable because the effect of simultaneously solving precipitation and bleaching fog becomes remarkable. The combined ratio of acetic acid and glycolic acid or lactic acid is preferably 1: 2 to 2: 1. The total amount of these acids used is suitably 0.5 mol or more per liter in a bleaching solution. It is preferably 1.2 to 2.5 mol / liter. More preferably, it is 1.5 to 2.0 mol / liter.

When the pH of the bleaching solution is adjusted to the above range, the above-mentioned acid and alkaline agents (for example, aqueous ammonia, KOH,
NaOH, imidazole, monoethanolamine, diethanolamine) may be used in combination. Of these, ammonia water is preferable.

Further, as the alkaline agent used in the bleaching starter when the starting solution of the bleaching solution is adjusted from the replenisher,
It is preferable to use potassium carbonate, aqueous ammonia, imidazole, monoethanolamine or diethanolamine. Further, the replenisher may be diluted and used as it is without using a bleaching starter.

In the present invention, various bleaching accelerators can be added to the bleaching solution or its prebath. Such bleaching accelerators are described, for example, in US Pat. No. 3,89.
No. 3,858, German Patent No. 1,290,821
No. 1,138,842, JP-A-53-95630 and Research Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulfide group, Thiazolidine derivatives described in JP-A-50-140129, thiourea derivatives described in U.S. Pat. No. 3,706,561, iodides described in JP-A-58-16235, German Patent No. 2 , 748,430, polyethylene oxides, JP-B-45-8836
It is possible to use the polyamine compounds described in the publication. Particularly preferred are mercapto compounds as described in British Patent 1,138,842 and Japanese Patent Application No. 1-111256.

In the bleaching solution of the present invention, in addition to the bleaching agent and the above-mentioned compound, a re-formation of bromide such as potassium bromide, sodium bromide, ammonium bromide or chloride such as potassium chloride, sodium chloride and ammonium chloride. A halogenating agent can be included. The concentration of the rehalogenating agent is 0.1 to 1 liter in the state of being used as the treatment liquid.
The amount is 5.0 mol, preferably 0.5 to 3.0 mol. Further, it is preferable to use ammonium nitrate as the metal corrosion inhibitor.

The bleaching time is 120 seconds or less, preferably 50 seconds or less, more preferably 40 seconds or less. In the treatment, it is preferable that the bleaching solution containing the ferric aminopolycarboxylic acid complex salt is subjected to aeration to oxidize the produced iron (II) aminopolycarboxylic acid complex salt. As a result, the oxidant is regenerated and the photographic performance is kept extremely stable. For the treatment with the bleaching solution in the present invention, it is preferable to carry out so-called evaporation correction by supplying water corresponding to the amount of evaporation of the processing solution. In particular, it is preferable in a color developing solution or a bleaching solution containing a high potential bleaching agent. The specific method for replenishing such water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed to monitor. Calculate the evaporation amount of water in the aquarium,
A method of calculating the evaporation amount of water in the bleaching tank from the evaporation amount of this water and replenishing the bleaching tank with water in proportion to this evaporation amount, or Japanese Patent Application Nos. 2-46743, 2-47777 and 2-47777.
47778, 2-47779, 2-11797.
The evaporation correction method using a liquid level sensor or an overflow sensor described in No. 2 specification is preferable.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. It is commonly used, especially ammonium thiosulfate being the most widely used. Further, the combined use of thiosulfate with thiocyanate, thioether compound, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, for the purpose of stabilizing the liquid, it is preferable to add various aminopolycarboxylic acids and chelating agents such as organic phosphonic acids. Preferred chelating agents are 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexane. Diamine tetraacetic acid, 1,2
Mention may be made of propylenediaminetetraacetic acid. Among these, 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid are particularly preferable. The fixing solution and the bleach-fixing solution have a pKa of 6.
It is preferable to contain a compound of 0 to 9.0. For example, it is preferable to add imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole in an amount of 0.1 to 10 mol / liter. The imidazole compound represents imidazole and its derivatives, and preferable substituents of imidazole include an alkyl group, an alkenyl group, an alkynyl group, an amino group, a nitro group, a halogen atom and the like.
The alkyl group, alkenyl group and alkynyl group may be further substituted with an amino group, a nitro group, a halogen atom or the like. The preferred total carbon number of the substituents of the imidazole is 1 to 6, and the most preferred substituent is the methyl group.

Specific examples of the imidazole compound are shown below, but the invention is not limited thereto. Imidazole 1-Methylimidazole 2-Methylimidazole 4-Methylimidazole 4- (2-Hydroxyethyl) -imidazole 2-Ethylimidazole 2-Vinylimidazole 4-Propylimidazole 4- (2-Aminoethyl) imidazole 2,4-Dimethylimidazole 2-Chloroimidazole Among these, preferred compounds are imidazole, 2-methyl-imidazole and 4-methyl-imidazole,
The most preferred compound is imidazole.

When the replenishing system is adopted in the processing of the present invention, the replenishing amount of the fixing solution is 10 per 1 m ² of the light-sensitive material.
0-3000 ml is preferred, but more preferably 300-
It is 1800 ml. In the present invention, the total processing time of the desilvering process consisting of a combination of bleaching, bleach-fixing and fixing is preferably 30 seconds to 3 minutes, more preferably 45 seconds to 2 minutes. The treatment temperature is 30 to 60 ° C., preferably 4
It is 0 to 55 ° C.

The processing solution having fixing ability of the present invention can be subjected to silver recovery by a known method, and the reclaimed solution subjected to such silver recovery can be used. As a silver recovery method,
Electrolysis method (described in French Patent No. 2,299,667),
Precipitation method (JP-A-52-73037, German Patent Nos. 2 and 3)
No. 31,220), an ion exchange method (JP-A-51-1)
7114, German Patent No. 2,548,237) and metal substitution method (UK Patent No. 1,353,805).
Etc. are effective. These silver recovery methods are preferable when they are carried out in-line from the tank solution because the suitability for rapid processing is further improved.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, there is a method described in JP-A-62-183460, in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material, and JP-A-6-62.
No. 183,461 rotating means to improve the stirring effect, and further, by moving the light-sensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface to make the emulsion surface turbulent There are a method of improving the effect and a method of increasing the circulation flow rate of the whole processing solution. Such a stirring improving means is effective in any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator.

After the processing step having fixing ability, usually,
Perform a washing process. After processing with a processing solution with fixing ability,
It is also possible to use a simple treatment method in which a stabilizing treatment using a stabilizing solution is carried out without substantially washing with water. The washing water used in the washing step and the stabilizing solution used in the stabilizing step are for preventing unevenness of water droplets when the photosensitive material after processing is dried.
Various surfactants can be included. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added.
Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

The washing water and the stabilizing solution may contain various antibacterial agents and antifungal agents in order to prevent water stains and molds generated on the processed light-sensitive material. Further, it is preferable to add various chelating agents to the wash water and the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetraacetic acid and diethylenetriamine-N, N, N ', N'-tetramethylene. Examples thereof include organic phosphonic acids such as phosphonic acid, and hydrolysates of maleic anhydride polymers described in European Patent 345172A1. It is also preferable that the preservative that can be contained in the fixing solution or the bleach-fixing solution is contained in the washing water and the stabilizing solution.

The stabilizing solution used in the stabilizing step is a processing solution for stabilizing the dye image, such as an organic acid or pH 3 to 10.
A liquid having a buffering capacity of 6, a liquid containing an image stabilizer such as an aldehyde (eg, formalin or glutaraldehyde), and the like can be used. The stabilizing solution may contain all compounds that can be added to the washing water, and in addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al,
Optical brighteners, hardeners, alkanolamines described in US Pat. No. 4,786,583 and the like can be used.

In the present invention, it is preferred that the stabilizing solution contains substantially no formaldehyde. The term "substantially free of formaldehyde" means that the total amount of free formaldehyde and its hydrate is 0.003 mol or less per liter of the stabilizing solution. By using such a stabilizing solution, it is possible to suppress the scattering of formaldehyde vapor during processing. Examples of the image stabilizer for controlling the free formaldehyde concentration include benzaldehydes such as m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, dimethylolurea and N. -N-methylol compounds such as methylolpyrazole and azolylmethylamines such as N, N'-bis (1,2,4-triazol-1-ylmethyl) piperazine. These image stabilizers are disclosed in JP-A-2-153348, 4-270344, 4-
No. 313753 (Corresponding European Patent Publication No. 504609A)
No. 2), No. 4-359249 (corresponding to European Patent Publication No. 519190A2), No. 5-34889, European Patent Publication No. 521477A1 and the like. In the present invention, the content of the image stabilizer is preferably 0.001 to 0.1 mol, and 0.0
01 to 0.05 mol is more preferable.

The pH of the stabilizing solution is preferably 6-9, more preferably 6.5-8. The washing step and the stabilizing step are preferably a multi-stage AC system, and the number of stages is preferably 2 to 4. The replenishing amount is 1 to 50 times, preferably 1 to 30 times, and more preferably 1 to 10 times the amount carried in from the previous bath per unit area.

As the water used in these washing step and stabilizing step, tap water can be used, but water, halogen, and ultraviolet rays deionized to have Ca and Mg ion concentrations of 5 mg / liter or less with an ion exchange resin or the like. It is preferable to use water that has been sterilized by a germicidal lamp or the like. The water for correcting the evaporation of each treatment liquid may be tap water, but it is preferable to use deionized water or sterilized water which is preferably used in the above washing step. In addition, it is preferable to use a method in which the overflow liquid of the water washing step or the stabilization step is allowed to flow into a bath having a fixing ability, which is a pre-bath, because the amount of waste liquid can be reduced.

In the process of the present invention, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenisher in order to correct the concentration due to evaporation. The specific method for replenishing water is not particularly limited, but among them, JP-A 1-2
A monitor water tank different from the bleaching tank described in Nos. 54959 and 1-254960 is installed, the evaporation amount of water in the monitor water tank is obtained, and the evaporation amount of water in the bleaching tank is calculated from the evaporation amount of this water. However, a method for replenishing the bleaching tank with water in proportion to this evaporation amount and Japanese Patent Application Nos. 2-46743 and 2-477.
The evaporation correction method using a liquid level sensor or an overflow sensor described in Nos. 77, 2-47778, 2-47779, and 2-117792 is preferable.

The light-sensitive material of the present invention may have at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer of a silver halide emulsion layer on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red color-sensitive layer and the green color. The color-sensitive layer and the blue color-sensitive layer are installed in this order.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-11343.
No. 8, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound and the like, and contains a color mixing inhibitor as commonly used. You can leave.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of two layers, a high-sensitivity emulsion layer and a low-sensitivity emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. Can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition, JP-A-57-11275
1, No. 62-200350, No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer on the side farther from the support and a high-sensitivity emulsion layer on the side closer to the support. May be installed.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, blue-sensitive layers / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity,
The middle layer is a silver halide emulsion layer having a lower photosensitivity, and the lower layer is a silver halide emulsion layer having a lower photosensitivity than that of the middle layer. An arrangement composed of three layers can be mentioned. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion layer from the side distant from the support in the same color-sensitive layer. / High-speed emulsion layer / low-speed emulsion layer may be arranged in this order.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat.
05,744, 4,707,436, JP-A-62-160448, 63-8
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of a main photosensitive layer such as BL, GL, and RL, described in JP-A 9850, adjacent to or in proximity to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or iodochloroodor containing about 0.5 to 30 mol% of silver iodide. It is silver oxide. Particularly preferred is about 2 mol% to about 10
Silver iodobromide or silver iodochlorobromide containing up to mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 μm or less, large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.
The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 17643 (1978 12
Mon), pp. 22-23, "I. Emulsion preparation
and types) ”, and No. 18716 (November 1979), 648.
Pp. No. 307105 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography", published by Paul Montel (P. Glafkides, Chimie et Physique Photographique,
Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin,
Published by Focal Press (GF Duffin, Photographic E
mulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., VL Zelikman et al., Making and Coating Photog.
It can be prepared using the method described in raphic Emulsion, Focal Press, 1964) and the like.

Monodispersed emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. The tabular grains are
Gatov, Photographic Science and
Engineering (Gutoff, Photographic Science and
Engineering, 14: 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048,
It can be easily prepared by the method described in U.S. Pat. No. 4,439,520 and British Patent No. 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed, or a type having a latent image both on the surface and inside. Must be a type of emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. The light-sensitive material of the present invention comprises two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion.
It can be used by mixing in the same layer.

Surface-fogged silver halide grains described in US Pat. No. 4,082,553, US Pat. No. 4,626,498.
No. 59, JP-A-59-214852, the inside of which is covered with silver halide grains and colloidal silver are preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. it can. The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat.
626,498 and JP-A-59-214852.

The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.75 μm,
In particular, 0.05 to 0.6 μm is preferable. The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are ± 40% of the average grain size). %) Is preferable).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The silver coating amount of the light-sensitive material of the present invention is 6.0 g / m ²
The following is preferable, and 4.5 g / m ² or less is the most preferable.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column, page 866 to 868 Color sensitizer ~ page 649 right column 4.whitening agent page 24 647 page right column 868 5.fogging prevention page 24-25 page 649 right column 868 ~ 870 agent, stabilizer 6.light absorber, 25 ~ Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 10. Binder 26 pages 651 left column 873 to 874 11. Plasticizer, page 27 650 pages right column 876 Lubricants 12. Coating aids , Pages 26-27, page 650, right column, pages 875-876, surface active agent, 13. static, page 27, page 650, right column, pages 876-877, inhibitors, matting agents, pages 878-879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add to the light-sensitive material a compound capable of being immobilized by reacting with formaldehyde described in 4,435,503. In the light-sensitive material of the present invention, U.S. Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28355.
It is preferable that the mercapto compound described in No. 1 is contained.

To the light-sensitive material of the present invention, a fog agent, a development accelerator, a silver halide solvent or a precursor thereof described in JP-A 1-106052, irrespective of the amount of developed silver produced by the development processing. It is preferable to include a releasing compound. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or Japanese Patent Publication No. 1-502912 or European Patent No. 317,308A, U.S. Patent No. 4,420,555, JP-A 1-259358. It is preferable to include the dyes described in No.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure Nos. 17643, VII-CG, and No. 307105, mentioned above.
It is described in the patents described in VII-C to G. Examples of the yellow coupler which can be used in combination with the yellow coupler represented by the general formula (1) of the present invention include, for example, US Pat.
3,501, 4,022,620, 4,326,024, 4,401,752
No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,4
25,020, 1,476,760, U.S. Pat.No. 3,973,968,
4,314,023, 4,511,649, European Patent 249,473A,
And the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897, and European Patent 73,636,
U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3
3552, Research Disclosure No. 24230 (1984
June), JP-A-60-43659, 61-72238, 60-357.
No. 30, No. 55-118034, No. 60-185951, U.S. Pat.
0,630, 4,540,654, 4,556,630, international publication WO8
Those described in 8/04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
2,212, 4,146,396, 4,228,233, 4,296,200
No., No. 2,369,929, No. 2,801,171, No. 2,772,162,
No. 2,895,826, No. 3,772,002, No. 3,758,308, No. 4,3
34,011, 4,327,173, West German Patent Publication 3,329,729
No., European Patent Nos. 121,365A, 249,453A, U.S. Patent No.
3,446,622, 4,333,999, 4,775,616, 4,45
1,559, 4,427,767, 4,690,889, 4,254,212
Nos. 4,296,199 and JP-A-61-242658 are preferred. Furthermore, JP-A-64-553, JP-A-64-554,
Pyrazoloazole couplers described in 64-555 and 64-556 and imidazole couplers described in U.S. Pat. No. 4,818,672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820, 4,080,211 and 4,36.
7,282, 4,409,320, 4,576,910, British Patent 2,1
No. 02,137 and European Patent No. 341,188A.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,125,5.
70, European Patent 96,570, West German Patent (Publication) 3,234,
Those described in No. 533 are preferable. Colored couplers for correcting unwanted absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G, and No. 307105.
Section VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413
Nos. 4,004,929, 4,138,258 and British Patent 1,146,368 are preferred. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye capable of reacting with a developing agent described in U.S. Pat.No. 4,777,120 to form a dye. It is also preferable to use a coupler having a precursor group as a leaving group.

Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention.
The DIR coupler which releases the development inhibitor is the above-mentioned RD N
Patents described in o.17643, VII-F and No. 307105, VII-F, JP-A-57-151944, 57-154234 and 60.
-184248, 63-37346, 63-37350, U.S. Patent No.
Those described in 4,248,962 and 4,782,012 are preferable.

RD No. 11449, RD No. 24241, JP-A-61-20
The bleaching accelerator releasing coupler described in 1247 etc. is effective for shortening the time of the processing step having a bleaching ability, and particularly when added to a light-sensitive material using the tabular silver halide grains described above, The effect is great. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,131,188, JP-A-59
-157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A 1-4494.
Compounds releasing a fogging agent, a development accelerator, a silver halide solvent, etc. by an oxidation-reduction reaction with an oxidized product of a developing agent described in No. 0 and No. 1-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,338,3.
93, 4,310,618 and the like, multiequivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIs described in JP-A-60-185950 and 62-24252.
R redox-releasing redox compounds, EP 173,30
Nos. 2A and 313,308A, couplers that release dyes that recolor after separation, ligand-releasing couplers described in U.S. Pat.No. 4,555,477, and couplers that release leuco dyes described in JP-A-63-75747. , A coupler releasing a fluorescent dye described in U.S. Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylazese) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline and the like), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene and the like) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Above about 160 ℃ organic solvent can be used, typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

The steps and effects of the latex dispersion method and specific examples of latex for impregnation are described in US Pat. No. 4,199,363,
It is described in West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, 1,2-benzisothiazolin-3-one described in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941 are used. Add various preservatives or mildewcides such as n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole. Is preferred.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. No. 17643, page 28, No. 18716, page 647, right column to page 648, left column, and No. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and 16 μm or less. Particularly preferred. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and 55% relative humidity (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art.
For example, Photographic Science and Engineering (Ph
otogr. Sci. & Eng.), No. 19, No. 2, pp. 124-129, by using a swellometer of the type described in
It can be measured, and T _1/2 is the time required to reach 1/2 of the saturated film thickness, where 90% of the maximum swollen film thickness reached when processed with a color developer at 30 ° C. for 3 minutes and 15 seconds is the saturated film thickness. It is defined as

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or by changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is preferably 150 to 500%.

The support of the color negative film used in the present invention is described in International Publication WO90 / 04205.
FIG. Those having the magnetic recording layer described in 1A are preferable. The support having such a magnetic recording layer preferably has a conductive layer containing zinc, titanium, tin or the like on one surface as described in JP-A-4-62543. Further, the one having the stripe magnetic recording layer described in JP-A-4-124628 and having the transparent magnetic recording layer adjacent to the stripe magnetic recording layer can also be used. A protective layer described in JP-A-4-73737 may be provided on the magnetic recording layer.

The thickness of the support is preferably 70 to 130 μm, particularly preferably 80 to 120 μm. As the material for the support, various plastic films described in JP-A-4-124636, page 5, upper right column, line 1 to page 6, upper right column, line 5 can be used, and preferred examples include cellulose derivatives (for example, diacetyl). -, Triacetyl-, propionyl-, butanoyl-, acetylpropionyl-acetate) and polyesters described in JP-B-48-40414 (for example, polyethylene terephthalate, poly-1,4-).
Cyclohexane dimethylene terephthalate, polyethylene naphthalate).

The support of the film used in the present invention is
Preferable are polyethylene terephthalate and polyethylene naphthalate described in Functional Materials, February 1991, pages 20 to 28, since a higher draining effect can be obtained and the mixing of pre-bath components in the next step can be reduced. .

The package (patrone) for accommodating the color negative film of the present invention may be any currently used or publicly known one, but particularly US Pat. No. 4,834,30.
No. 6, FIG. 1-FIG. The shape described in 3 or
U.S. Pat. No. 4,846,418, FIG. 1-FI
G. Those described in 3 are preferable.

The format of the color negative film used in the present invention is the Japanese Industrial Standard "JIS.K-7519".
(1982) ”, any known one can be used, but the format having a small number of perforations and a narrow width described in JP-A-4-287040 has a small amount of processing solution taken out and a low replenishment. It is preferable because it is suitable for rapid processing.

In processing a film having such a format, it is preferable to use a jet agitation method in which a jet of the processing liquid collides with the film surface.

[0160]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.11 ExF-1 3.4 × 10 ^-3 HBS-1 0.16

Second layer (intermediate layer) ExC-2 0.030 UV-1 0.020 UV-2 0.020 UV-3 0.060 HBS-1 0.05 HBS-2 0.020 Polyethyl acrylate latex 0.080 Gelatin 0.90

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.19 Emulsion B Silver 0.19 ExS-1 5.0 × 10 ^-4 ExS-2 1.8 × 10 ^-5 ExS-3 5.0 × 10 ^-4 ExC-1 0.050 ExC-3 0.030 ExC-4 0.14 ExC-5 3.0 x 10 ^-3 ExC-7 1.0 x 10 ^-3 ExC-8 0.010 Cpd-2 0.005 HBS-1 0.10 Gelatin 0.95

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion C Silver 0.60 ExS-1 3.4 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 ExC-1 0.15 ExC-2 0.060 ExC-4 0.050 ExC-5 0.010 ExC-8 0.010 Cpd-2 0.023 HBS-1 0.11 Gelatin 0.60

Fifth Layer (High Sensitive Red Sensitive Emulsion Layer) Emulsion D Silver 1.54 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC-1 0.10 ExC-3 0.050 ExC-5 2.0 × 10 ^-3 ExC-6 0.010 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.20 HBS-2 0.10 Gelatin 1.30 6th layer (intermediate layer) Cpd-1 0.090 HBS-1 0.05 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion E Silver 0.24 Emulsion F Silver 0.24 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-1 5.0 × 10 ^-3 ExM-2 0.28 ExM-3 0.086 ExM-4 0.030 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.85

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion G Silver 0.94 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.14 ExM-3 0.045 ExM-5 0.020 ExY-1 7.0 × 10 ^-3 ExY-4 2.0 × 10 ^-3 ExY-5 0.020 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion H Silver 1.29 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.050 ExM-5 0.020 ExY-4 5.0x10 ^-3 Cpd-3 0.050 HBS-1 0.20 HBS-2 0.08 Polyethyl acrylate latex 0.26 Gelatin 1.45

10th layer (yellow filter layer) Yellow colloidal silver Silver 7.5 × 10 ^-3 Cpd-1 0.13 Cpd-4 7.5 × 10 ^-3 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue emulsion layer) Emulsion I Silver 0.25 Emulsion J Silver 0.25 Emulsion K Silver 0.10 ExS-7 8.0 × 10 ^-4 ExC-7 0.010 ExY-1 5.0 × 10 ^-3 ExY-2 0.70 ExY-1 4.5 × 10 ^-3 ExY-6 0.09 HBS-1 0.25 Gelatin 1.55

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Emulsion L Silver 1.30 ExS-7 3.0 × 10 ^-4 ExY-2 0.17 ExY-1 4.0 × 10 ^-3 Cpd-2 0.10 HBS-1 0.050 Gelatin 1.15

Thirteenth layer (first protective layer) UV-2 0.10 UV-3 0.12 UV-4 0.30 HBS-1 0.10 Gelatin 2.50

14th layer (second protective layer) Emulsion M Silver 0.10 H-1 0.32 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt, palladium salt, and rhodium salt. Cpd-4 was dispersed in a solid state according to the method described in International Patent No. 88-4794.

[0175]

[Table 1]

In Table 1, (1) Emulsions I to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to L were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) In the tabular grains, dislocation lines as described in JP-A-3-237450 are observed using a high voltage electron microscope.

The couplers and additives of each layer were dispersed in a gelatin solution by the method shown in Table 2. The addition method for each layer is shown in Table 3.

[0178]

[Table 2]

[0179]

[Table 3]

[0180]

[Chemical 37]

[0181]

[Chemical 38]

[0182]

[Chemical Formula 39]

[0183]

[Chemical 40]

[0184]

[Chemical 41]

[0185]

[Chemical 42]

[0186]

[Chemical 43]

[0187]

[Chemical 44]

[0188]

[Chemical formula 45]

[0189]

[Chemical formula 46]

[0190]

[Chemical 47]

[0191]

[Chemical 48]

[0192]

[Chemical 49]

[0193]

[Chemical 50]

[0194]

[Chemical 51]

Samples 101 to 102 were prepared in the same manner as in Sample 101 except that the yellow couplers (ExY-2) of the 11th and 12th layers of Sample 101 were changed in equimolar amounts to the comparative coupler or the coupler of the present invention as shown in Table 4. 116 was produced.

[0196]

[Table 4]

[0197]

[Chemical 52]

Imagewise exposing these samples to white light,
Processing was performed using an automatic developing machine until the replenishment amount of the color developing solution became three times the tank volume. The treatment process and the treatment liquid composition are shown below.

(Processing method) Process processing time Processing temperature Replenishment amount * Tank capacity Color development 2 minutes 30 seconds 38.0 ℃ 600 ml 5 liters Bleach 50 seconds 38.0 ℃ 130 ml 1 liter Bleach fixing 50 seconds 38.0 ℃ ――― 1 liter Settling 50 seconds 38.0 ℃ 420 ml 1 liter Washing with water 30 seconds 38.0 ℃ 880 ml 0.6 liter Stability (1) 20 seconds 38.0 ℃ ――― 0.6 liter Stability (2) 20 seconds 38.0 ℃ 520 ml 0.6 liter Dry 1 Minute 30 seconds 60 ° C * The replenishing amount is a countercurrent system from (2) to (1) for the stabilizing solution per 1 m ² of the light-sensitive material, and the overflow solution of washing water is all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the water washing process are each per 1 m ² of the light-sensitive material. 70ml, 60ml,
It was 60 ml and 60 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.2 4.2 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] -aniline (ExD-1) sulfate (developing agent) 16 mmol 20 mmol Water was added. 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.15

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropaneferric Acid Ferric Acid Ammonium Monohydrate 130 195 Ammonium Bromide 70 105 Ammonium Nitrate 14 21 Hydroxyacetic Acid 25 38 Acetic Acid 40 60 Water Add 1.0 liter 1.0 liter pH (adjusted with ammonia water) 4.6 4.4

(Bleaching / fixing tank liquid) A 15:85 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid. (P
H 7.0)

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / liter) 280 liter 840 liter Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water 1.0 liter 1.0 liter pH (Adjust with ammonia water and acetic acid) 7.4 7.45

(Rinsing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas Co.).
120B) and an OH type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg /
Treated to less than 1 liter, followed by 20 mg / liter sodium diisocyanurate dichloride and 150 m sodium sulfate
g / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Stabilizing Solution) Tank Solution and Replenishing Solution Common (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2-Benzisothiazolin-3-one 0.03 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

Further, the developing agent ExD- in the color developing solution is used.
1 was changed to each developing agent shown in Tables 5 and 6 in an equimolar amount, and the same processing was performed. After the processing, the characteristics of each sample were measured by blue light, and the yellow density at the exposure amount at which the yellow density when the sample 101 was processed with the ExD-5 color developing solution was 1.6 was determined. The results obtained are shown in Tables 5 and 6
Shown in.

[0207]

[Table 5]

[0208]

[Table 6]

From the results shown in Tables 5 and 6, it can be seen that high color density can be obtained by treating the light-sensitive material of the present invention with the developer containing the developing agent of the present invention. This tendency was also observed in the comparative yellow coupler, but it was more remarkable in the coupler of the present invention, and the effect more than expected was obtained. Further, the difference between the yellow density of the unexposed portion of each sample and the yellow density when the same processing was performed without passing only the color development step of the above processing step (yellow stain due to bleaching fog) was determined. The results obtained are shown in Tables 7 and 8.

[0210]

[Table 7]

[0211]

[Table 8]

From these results, the yellow stain due to bleaching fog was very large, especially when the color developing agent of the present invention was used, but it was surprisingly reduced by the coupler of the present invention, that is, the color developability was high and the bleaching fog was high. And an image forming method with a small yellow stain was obtained.

Further, when the amount of the comparative developing agent (ExD-1) added was increased so that the yellow densities in the high-exposed areas became equal in the same color developing time as that of the developing agent of the present invention, bleaching fog occurred. The yellow stain is remarkably increased and is worse than that of the image forming method of the present invention.

Example 2 Processing was carried out in the same manner as in the processing method of Example 1 except that the replenishing amount and the composition of the replenishing solution in the bleaching step were changed as shown in Table 9. After the treatment, the yellow stain due to bleaching fog was determined in the same manner as in Example 1. The results obtained are shown in Tables 10 and 11.

[0215]

[Table 9]

[0216]

[Table 10]

[0217]

[Table 11]

From these results, when the color developing agent of the present invention is used, the yellow stain is remarkably increased by reducing the replenishing amount in the bleaching step, but the yellow coupler of the present invention improves the yellow stain and improves the yellow stain. It can be seen that the effect of the present invention is greater when the replenishment amount is reduced. It should be noted that, in any of the treatments, excellent color development was exhibited.

Further, these samples were tested at 60 ° C. and a relative humidity of 7
After storage for 2 months under the condition of 0%, the yellow density was measured again, and the difference from the density immediately after the processing in the yellow density of the unexposed area was obtained to evaluate the color development over time. The color formation with time is related to the amount of the residual main agent in the light-sensitive material after the light-sensitive material has passed through all the processing steps, but the color formation with time was small and an improvement was observed in the image forming method of the present invention.

Further, it is generally known that if the replenishing amount in the bleaching step is reduced, desilvering failure is likely to occur, but the amount of silver remaining (mg / m ² ) in the sample by the fluorescent X-ray method.
It was confirmed that the desilvering performance was not impaired even when the replenishing amount in the bleaching step was reduced in the image forming method of the present invention.

Example 3 The same treatment as in Example 1 was carried out as follows.

Processing process (Process) (Processing time) (Processing temperature) (Replenishment amount) (Tank capacity) Color development 60 seconds 45.0 ℃ 140 ml / m ² 2.0 liters Bleach fixing 60 seconds 45.0 ℃ 120 ml / m ² 2.0 liters Washing with water (1) 15 seconds 45.0 ℃ ―― 0.5 liters Washing with water (2) 15 seconds 45.0 ℃ ―― 0.5 liters Washing with water (3) 15 seconds 45.0 ℃ 120 ml / m ² 0.5 liters Stability 2 seconds Room temperature smearing Dry Drying 20 seconds 85 ° C Crossover time from color development to bleach-fixing and bleach-fixing to water washing (1) is 5 seconds. The average carry-out amount of the processing liquid per 1 m ^{2 of the} light-sensitive material is 40 ml. Washing with water (1)
~ (3) is a countercurrent multistage cascade system. Washing with water (1)
(3) was carried out by a multi-chamber washing method in which the wiper blade was capable of moving in liquid without crossover. The total processing time is 2 minutes 47 seconds. Further, as described in JP-A-3-280042, the temperature and humidity of the outside air of the processor were detected by a thermo-hygrometer in each tank to correct the evaporation by converting the evaporation amount. Ion-exchanged water for washing water was used as the water for evaporation correction.

The composition of the treatment liquid used in each step is shown below. (Color developer) Mother liquor Replenisher Diethylenetriaminepentaacetic acid 4.0 g 4.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 g 3.0 g Potassium hydroxide 10.0 g 15.0 g Potassium iodide 1.3 g 0 g Potassium bromide 4.2 g 0 g Potassium carbonate 50.0g 50.0 g Sodium sulfite 4.0 g 6.8 g Hydroxylamine 50.0 mmol 80.0 mmol Color developing agent (ExD-1) 40.0 mmol 55.0 mmol Water was added to 1000 ml 1000 ml pH 10.10 11.80

(Bleaching Fixing Solution) Mother Liquor Replenishing Solution Bleaching Agent (Ferric Ammonium Salt of Compound A) 0.15 mol 0.20 mol Ethylenediaminetetraacetic Acid Ferric Ammonium Dihydrate 0.05 mol 0.07 mol Sulfinic Acid (Compound B) 0.1 mol 0.15 mol Fixing accelerator (Compound C) 0.3 mol 0.4 mol Ammonium thiosulfate (75%) 300 ml 400 ml Ammonium sulfite 30 g 45 g Succinic acid 30 g 40 g Water is added 1000 ml 1000 ml pH

[0225]

[Chemical 53]

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Stabilizer) Common to mother liquor and tank liquid Sodium p-toluenesulfinate 0.03 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 g Ethylenediaminetetraacetic acid disodium salt 0.05 g Water was added. 1000 ml pH 8.0

The bleach-fix solution was subjected to in-line silver recovery with a silver recovery device. The silver recovery device is a small electrolytic silver recovery device with an anode of carbon and a cathode of stainless steel drum.
A current density of 0.5 A / dm ² was used. In the above processing steps, continuous processing was carried out until the replenishing amount of the bleach-fixing solution became 3 times the tank capacity. Further, the developing agent in the color developing solution was replaced with the developing agent of the present invention in an equimolar amount, and the same treatment was carried out to obtain yellow stain due to bleaching fog in the same manner as in Example 1. Yellow stain due to bleaching fog is remarkably increased with shortening of processing time (total processing time is within 3 minutes) and low replenishment of bleach-fixing step, but yellow stain due to bleaching fog is improved by the image forming method of the present invention. Moreover, a high color density was obtained in a short time, and an image excellent in color reproducibility was obtained.

[0229]

According to the color image forming method of the present invention, the color reproducibility is excellent in a short color developing time, and particularly, even if the replenishing amount of the processing solution containing the bleaching agent is reduced, the yellow stain is small, A color image having excellent desilvering property can be formed.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Masato Taniguchi 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material containing at least one yellow coupler represented by the following general formula (1) in at least one silver halide emulsion layer provided on a support: The following general formula (D1) or (D
2. A color image forming method, which comprises performing color development in the presence of at least one p-phenylenediamine color developing agent represented by 2). General formula (1) R ¹ OCOCH (X) CONR ² R ^{3 In} formula (1), R ¹ represents an alkyl group, an aryl group or a heterocyclic group, and R ² is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Represents a group, R ³ represents an alkyl group, an aryl group or a heterocyclic group, and X represents a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Here, R ² and R ³ may combine with each other to form a ring. [Chemical 1] In formula (D1), R ₁ is a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight-chain or branched chain having 2 to 8 carbon atoms in the main chain. Represents a hydroxyalkyl group. R ₂ is a straight-chain or branched unsubstituted alkylene group having a main chain of 3 to 8 carbon atoms and having a total of 3 to 8 carbon atoms, or a total number of carbon atoms having a main chain of 3 to 8 carbon atoms is 3 Represents a linear or branched hydroxyalkylene group of -8. R ₃ represents a linear or branched alkyl group having 1 to 4 carbon atoms. [Chemical 2] In formula (D2), when R ₄ represents a hydroxyalkyl group having a total carbon number of 2 or more, R ₅ also represents a hydroxyalkyl group having a total carbon number of 2 or more, and R ₆ represents an alkyl group. However, R ₄ and R ₅ may be the same or different,
The total number of carbon atoms possessed by R ₄ , R ₅ and R ₆ is 10 or less. When R ₄ represents an unsubstituted alkyl group having 1 to 3 carbon atoms, R ₅ represents an alkyl group having at least two hydroxy groups, and R ₆ represents an alkyl group having 1 to 4 carbon atoms. 2. A method of processing with a processing solution having a bleaching ability after color development according to claim 1, wherein the replenishing amount of the processing solution is 45 ml to 500 ml per 1 m ^{2 of the} light-sensitive material. A method of processing a silver halide color photographic light-sensitive material.