JPH04355751A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce fogging and fluctuation of photographic characteristics and to obtain sufficient color developing performance by processing the silver halide color photographic sensitive material containing an acylacetamide type yellow coupler with a specified developing solution. CONSTITUTION:The silver halide color photographic sensitive material containing at least one of the acylacetamide type yellow couplers represented by formula I us developed with a developing solution containing a Cl<-> concentration of >=0.08 mol/l within a developing time of 50 sec and at a temperature of >=36 deg.C. In formula I, R1 is not H but a monovalent group and does not form a ring; and Q is a nonmetallic atomic group necessary to form a 3- or 5-membered hydrocarbon ring or hetero ring containing at least one of N, S, O, and P together with the C atom. This color photographic sensitive material contains silver chloride in a concentration as high as >=90mol% in at least one of emulsion layers.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a processing method for silver halide color photographic light-sensitive materials, and in particular, to a processing method that provides excellent photographic properties such as minimal fog and maximum density in rapid processing, and moreover stable photographic properties. Regarding how it can be maintained.

BACKGROUND ART In the processing method of silver halide color photographic light-sensitive materials, a technique of using a high silver chloride emulsion for the purpose of shortening the processing time and reducing pollution is disclosed in WO 87/04534 and JP-A-61 No. 70552. It is true that when a high silver chloride emulsion is used, the processing time is shortened, but on the other hand, the photographic properties fluctuate greatly due to pH oxidation of the color developer and changes in the concentration of the main ingredient.
On the low activity side, the maximum density of yellow especially decreases, and on the high activity side, yellow fog tends to occur, and a solution has been awaited.

[0002] In addition, Japanese Patent Application Laid-open Nos. 106655/1983 and 116639/1999 disclose techniques for processing high-silver chloride photosensitive materials with a color developer containing a high concentration of chloride ions. , when the chloride ion concentration increases,
Particularly in rapid processing, the fluctuations in the above-mentioned photographic properties become large, and a method that provides stable performance has been desired.

0003

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a processing method in which fog is reduced and sufficient color development is obtained in rapid processing, and fluctuations in photographic properties are significantly reduced.

0004

[Means for Solving the Problems] It has been found that the above object can be achieved by the following method. That is, (1) a silver halide color photographic light-sensitive material containing at least one type of acylacetamide type yellow coupler having an acyl group represented by the following general formula (I) was heated at 36°C for 50 seconds or less.
As described above, the method for processing a silver halide color photographic material is characterized in that it is developed with a developer having a chloride ion concentration of 0.08 mol/liter or more. General formula (I)

[Formula 2] (In the formula, R1 represents a monovalent group, Q together with C is 3
-Represents a group of nonmetallic atoms necessary to form a 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle having at least one heteroatom selected from N, S, O, and P in the ring. However, R1 is not a hydrogen atom and does not combine with Q to form a ring. )

The compound of general formula (I) of the present invention will be explained in detail below. The acylacetamide type yellow coupler of the present invention is preferably represented by the following general formula [Y].

[0006]

[Chemical formula 3]

In formula [Y], R1 represents a monovalent substituent excluding a hydrogen atom, and Q together with C represents a 3- to 5-membered hydrocarbon ring or at least one hetero group selected from N, S, O, and P. R2 is a hydrogen atom, a halogen atom (F, Cl, Br, I. In the following description of formula [Y] ), an alkoxy group, an aryloxy group, an alkyl group, or an amino group, R3 is a group that can be substituted on the benzene ring, and X is a hydrogen atom or coupling with an oxidized product of an aromatic primary amine developer. A group capable of leaving by reaction (hereinafter referred to as a leaving group) is represented, and 1 represents an integer of 0 to 4. However, when l is plural, the plural R3's may be the same or different.

Here, as an example of R3, a halogen atom,
Alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, alkylsulfonyl group,
ureido group, sulfamoylamino group, alkoxycarbonylamino group, alkoxysulfonyl group, acyloxy group, nitro group, heterocyclic group, cyano group, acyl group, amino group, imide group, alkylsulfonyloxy group, arylsulfonyloxy group, There are carboxyl groups, sulfo groups, and hydroxyl groups (hereinafter referred to as substituent group A), and examples of leaving groups include heterocyclic groups, aryloxy groups, arylthio groups, acyloxy groups, and alkylsulfonyl groups that are bonded to the coupling active position at the nitrogen atom. There are oxy groups, arylsulfonyloxy groups, heterocyclic oxy groups, and halogen atoms.

[0009] When the substituent in formula [Y] is an alkyl group or contains an alkyl group, unless otherwise specified, the alkyl group is a linear, branched or cyclic group, even if it is substituted. Refers to an alkyl group that may contain an unsaturated bond.

When the substituent in formula [Y] is an aryl group or contains an aryl group, unless otherwise specified, the aryl group means an optionally substituted monocyclic or condensed ring aryl group.

[0011] When the substituent in formula [Y] is a heterocyclic group or contains a heterocyclic group, unless otherwise specified, the heterocyclic group is at least one selected from O, N, S, P, Se, Te. means a 3- to 8-membered optionally substituted monocyclic or condensed ring heterocyclic group containing 3 to 8 heteroatoms in the ring.

The substituents preferably used in formula [Y] will be explained below. In formula [Y], R1 is preferably a halogen atom, a cyano group, or a total number of carbon atoms (hereinafter abbreviated as C number) 1 to 3, which may be substituted.
0 monovalent group (e.g. alkyl group, alkoxy group) or a monovalent group having 6 to 30 carbon atoms (e.g. aryl group, aryloxy group), and its substituents include, for example, a halogen atom, an alkyl group, There are alkoxy groups, nitro groups, amino groups, carbonamide groups, sulfonamide groups, and acyl groups.

[0013] In formula [Y], Q preferably has 3 to 3 carbon atoms, which may be substituted with any of 3 to 5 members, together with C.
0 hydrocarbon ring or a group of nonmetallic atoms necessary to form a C2-30 heterocycle containing at least one heteroatom selected from N, S, O, and P in the ring. Also,
The ring formed by Q together with C may contain an unsaturated bond within the ring. Examples of rings that Q forms with C include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclopropene ring, cyclobutene ring, cyclopentene ring, oxetane ring, oxolane ring, 1,3-dioxolane ring, thietane ring, thiolane ring, and pyrrolidine. There is a ring. Examples of substituents include halogen atom, hydroxyl group, alkyl group, aryl group, acyl group, alkoxy group, aryloxy group,
Cyano group, alkoxycarbonyl group, alkylthio group,
It has an arylthio group.

In formula [Y], R2 is preferably a halogen atom, each of which may be substituted, and has 1 to 3 carbon atoms.
0 alkoxy group, C6-30 aryloxy group,
It represents an alkyl group having 1 to 30 carbon atoms or an amino group having 0 to 30 carbon atoms, and its substituents include, for example, a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.

In formula [Y], R3 is preferably a halogen atom, any of which may be substituted, and has 1 to 30 carbon atoms.
Alkyl group, C6-30 aryl group, C1-3
0 alkoxy group, C2-30 alkoxycarbonyl group, C7-30 aryloxycarbonyl group, C
Carbonamide group having 1 to 30 carbon atoms, sulfonamide group having 1 to 30 carbon atoms, carbamoyl group having 1 to 30 carbon atoms, 0 to 30 carbon atoms
30 sulfamoyl group, C1-30 alkylsulfonyl group, C6-30 arylsulfonyl group, C1-30 ureido group, C0-30 sulfamoylamino group, C2-30 30 alkoxycarbonylamino group, C1-30 heterocyclic group, C1-30 acyl group, C1-30 alkylsulfonyloxy group, C6
-30 arylsulfonyloxy groups, and examples of its substituents include substituents selected from the above-mentioned substituent group A.

In formula [Y], l preferably represents an integer of 1 or 2, and the substitution position of R3 is:

[C4] The meta or para position is preferred.

In formula [Y], X preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active position through a nitrogen atom. When X represents a heterocyclic group,
is preferably a 5- to 7-membered monocyclic or fused heterocyclic group which may be substituted, examples of which include succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1, 2
, 4-triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole,
imidazolidine-2,4-dione, oxazolidine-2
, 4-dione, thiazolidine-2,4-dione, imidazolidin-2-one, oxazolidin-2-one, thiazolidin-2-one, benzimidazolin-2-one,
Benzoxazoline-2-one, benzothiazoline-2
-one, 2-pyrrolin-5-one, 2-imidazoline-
5-one, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-
Pyrimidone, 6-pyridazone-2-pyrazone, 2-amino-1,3,4-thiazolidine, 2-imino-1,3,
Examples include 4-thiazolidin-4-one, and these heterocycles may be substituted. Examples of these heterocyclic substituents include substituents selected from the above-mentioned substituent group A.

When X represents an aryloxy group, X preferably represents an aryloxy group having 6 to 30 carbon atoms,
When X is a heterocycle, it may be substituted with a group selected from the substituent groups listed above. Substituents for the aryloxy group include a halogen atom, a cyano group, a nitro group, a carboxyl group, a trifluoromethyl group, an alkoxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group,
An arylsulfonyl group or a cyano group is preferred.

Next, particularly preferably used substituents in formula [Y] will be explained. R1 is particularly preferably a halogen atom or an alkyl group, most preferably a methyl group. Q is particularly preferably a group of nonmetallic atoms forming a 3- to 5-membered hydrocarbon ring together with C, such as -[CR2]2-, -[CR2]3-
, -[CR2]4-. Here, R represents a hydrogen atom, a halogen atom or an alkyl group. However, a plurality of R's and CR2's may be the same or different. Most preferably, Q is -[CR2]2- which forms a three-membered ring together with the C to which it is bonded.

R2 is particularly preferably a chlorine atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms (eg, methyl, trifluoromethyl, ethyl, isopropyl, t-butyl).
, an alkoxy group having 1 to 8 carbon atoms (e.g. methoxy, ethoxy, methoxyethoxy, butoxy), or an alkoxy group having 6 to 2 carbon atoms
4 aryloxy groups (eg phenoxy group, p-tolyloxy, p-methoxyphenoxy), most preferably chlorine atom, methoxy group or trifluoromethyl group.

R3 is particularly preferably a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, or a sulfamoyl group, and most preferably an alkoxy group, an alkoxycarbonyl group, It is a carbonamide group or a sulfonamide group. X is particularly preferably a 5-membered heterocyclic group bonded to the coupling active position via the nitrogen atom (e.g. imidazolidine-2,4-dione-3-yl, oxazolidine-2,4-dione-3-yl).
yl) or aryloxy group, most preferably imidazolidine-2,4-dione-3-yl group.

The coupler represented by formula [Y] has substituents R1, Q, X or

[Image Omitted] In the formula 5, a dimer or a multimer of more than two molecules may be formed which are bonded to each other via a group having a valence of two or more. In this case, the number of carbon atoms in each substituent group may be outside the range specified above.

Specific examples of each substituent in formula [Y] are shown below.

[C6]

[0024]

[C7]

[0025]

[Chemical formula 8]

[0026]

[Chemical formula 9]

[0027]

[Chemical formula 10]

[0028]

[Chemical formula 11]

[0029]

[Chemical formula 12]

Specific examples of the yellow coupler represented by formula [Y] are shown below.

[Chemical formula 13]

[0031]

[Chemical formula 14]

[0032]

[Chemical formula 15]

[0033]

[Chemical formula 16]

[0034]

[Chemical formula 17]

[0035]

[Chemical formula 18]

[0036]

[Chemical formula 19]

[0037]

[C20]

[0038]

[C21]

[0039]

[C22]

[0040]

[C23]

The yellow coupler represented by the general formula [Y] is obtained by synthesizing the carboxylic acid represented by the general formula [A] and then using a conventionally known synthesis method (for example, JP-A-51-10263).
It can be synthesized by the synthesis method described in No. 6 specification).

[0042]

[C24]

The carboxylic acid represented by the general formula [A] is
J. Chem. Soc. (C), 1968, 25
48, J. Am. Chem. Soc. , 1934
, 56, 2710. Synthesis, 19
71, 258, J. Org. Chem. ,19
78, 43, 1729, CA, 1960, 66, 185
It can be synthesized by the method described in 33y et al.

Examples of the synthesis of the couplers of the present invention are shown below. Synthesis Example 1 Synthesis of Exemplary Compound Y-31 Gotkis,
D. etal, J. Am. Chem. Soc. ,193
1 synthesized by the method described in 4,56,2710
-38.1 g of oxalyl chloride was added dropwise to a mixture of 25 g of -methylcyclopropanecarboxylic acid, 100 ml of methylene chloride, and 1 ml of N,N-dimethylformamide at room temperature over 30 minutes. After the dropwise addition, the mixture was reacted at room temperature for 2 hours, and methylene chloride and excess oxalyl chloride were removed under reduced pressure using an aspirator to obtain an oily substance of 1-methylcyclopropanecarbonyl chloride.

[0045] 100 ml of methanol was added dropwise to a mixture of 6 g of magnesium and 2 ml of carbon tetrachloride at room temperature over a period of 30 minutes, then heated under reflux for 2 hours, and then 32.6 g of ethyl 3-oxobutanoate was added dropwise over a period of 30 minutes under heating under reflux. do. After the dropwise addition, the mixture was further heated under reflux for 2 hours, and methanol was completely distilled off under reduced pressure using an aspirator. 100 ml of tetrahydrofuran is added to the reactant to disperse it, and the previously obtained 1-methylcyclopropanecarbonyl chloride is added dropwise at room temperature. After reacting for 30 minutes, the reaction solution was mixed with 300 ml of ethyl acetate,
After extraction with dilute sulfuric acid water and washing with water, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 55.3 g of ethyl 2-(1-methylcyclopropanecarbonyl)-3-oxobutanoate as an oil. .

55 g of ethyl 2-(1-methylcyclopropanecarbonyl)-3-oxobutanoate, 1 ethanol
60 ml of the solution is stirred at room temperature, and 60 ml of 30% aqueous ammonia is added dropwise over 10 minutes. Thereafter, the mixture was stirred for 1 hour, extracted with 300 ml of ethyl acetate and diluted hydrochloric acid, neutralized, washed with water, and the organic layer was dried over anhydrous sodium sulfate. 43g was obtained.

(1-methylcyclopropanecarbonyl)
34 g of ethyl acetate and N-(3-amino-4-chlorophenyl)-2-(2,4-di-t-pentylphenoxy)
44.5 g of butanamide is heated to reflux at an internal temperature of 100 to 120° C. under reduced pressure using an aspirator. After 4 hours of reaction, the reaction solution was purified by column chromatography using a mixed solvent of n-hexane and ethyl acetate to obtain 49 g of Exemplified Compound Y-31 as a viscous oil. The structure of the compound is determined by MS spectrum, NMR
Confirmed by spectrum and elemental analysis.

Synthesis Example 2 Synthesis of Exemplified Compound Y-1 22.8 g of Exemplified Compound Y-31 was added to 300 m of methylene chloride.
5.4 g of sulfuryl chloride was added dropwise over 10 minutes under ice-cooling. After reacting for 30 minutes, the reaction solution was thoroughly washed with water, dried over anhydrous sodium sulfate, and concentrated to obtain the chloride of Exemplified Compound Y-25. 1-benzyl-5-ethoxyhydantoin 18.7g, triethylamine 11.2ml, N,N
- A solution of the chloride of the previously synthesized exemplary compound Y-31 dissolved in 50 ml of N,N-dimethylformaldehyde is added dropwise to a solution of 50 ml of dimethylformamide at room temperature over 30 minutes.

After reacting at 40° C. for 4 hours, the reaction solution was extracted with 300 ml of ethyl acetate, washed with water, washed with 300 ml of a 2% aqueous triethylamine solution, and then neutralized with diluted hydrochloric acid. After drying the organic layer over anhydrous sodium sulfate, the solvent was distilled off, and the resulting oil was crystallized from a mixed solvent of n-hexane and ethyl acetate. The precipitated crystals were filtered and n-
After washing with a mixed solvent of hexane and ethyl acetate, 22.8 g of crystals of Exemplified Compound Y-1 were obtained by drying. The structure of the compound was confirmed by MS spectrum, NMR spectrum, and elemental analysis. Moreover, the melting point was 132-133°C.

The amount of the coupler of general formula (I) used is:
The amount is in the range of 0.001 to 1 mol, preferably 0.01 to 0.5 mol, per 1 mol of photosensitive silver halide. Further, the compound of the present invention can be introduced into a photosensitive material by various known dispersion methods described below.

The present invention can be applied to any photosensitive material, and in addition to the compound of general formula (I), various additives can be added to the photographic constituent layers. For more information please refer to the following patent publications, in particular European Patent EP 0,355,66
0A2 (Japanese Patent Application No. 1-107011) is preferably used.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

[Table 4]

[0056]

[Table 5]

[0057] Also, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole cyan coupler described in No. 33144, European Patent EP 0,333,185A2
3-hydroxypyridine cyan coupler (
Among them, 4 of couplers (42) listed as specific examples
Particularly preferred are equivalent couplers with a chlorine leaving group to make them di-equivalent, couplers (6) and (9), and cyclic active methylene cyan couplers described in JP-A No. 64-32260 (especially preferred). Particular preference is given to the couplers examples 3, 8, 34 listed by way of example).

[0058] As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide, etc. can be used. In order to achieve this, it is preferable to use a silver chlorobromide or silver chloride emulsion which is substantially free of silver iodide and has a silver chloride content of 90 mol % or more, more 95% or more, especially 98% or more. Also,
In the photosensitive material according to the present invention, a hydrophilic colloid layer is incorporated into a hydrophilic colloid layer for the purpose of improving image sharpness, etc.
, 337, 490 A2, pages 27 to 76, dyes that can be decolorized by processing (especially oxonol dyes) are used when the optical reflection density at 680 nm of the photosensitive material is 0.
70 or more, or 12% by weight or more (more preferably 14 (wt% or more) is preferably contained.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservation improving compound as described in European Patent EP 0,277,589A2 together with a coupler. Particularly preferred is the combination with a pyrazoloazole coupler. That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent the generation of stains and other side effects due to the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

[0060] The photosensitive material according to the present invention is also treated with anti-mildew agents as described in JP-A No. 63-271247 in order to prevent various types of mold and bacteria that grow in the hydrophilic colloid layer and degrade images. It is preferable to add an agent. In addition, the support used in the light-sensitive material according to the present invention includes a white polyester support for displays or a support in which a layer containing a white pigment is provided on the support on the side having a silver halide emulsion layer. May be used. In order to further improve sharpness, it is preferable to coat an antihalation layer on the side on which the silver halide emulsion layer is coated or on the back side of the support. In particular, it is preferable to set the transmission density of the support in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low illuminance exposure or high illuminance short time exposure, and in the latter case in particular, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 -4 seconds is preferred.

[0062] Also, upon exposure, US Pat. No. 4,88
Preferably, a band stop filter as described in US Pat. No. 0,726 is used. This removes light color mixing,
Color reproducibility is significantly improved.

The processing of the present invention will be explained in detail below. In the present invention, the photographic material is subjected to color development, desilvering, and water washing (or stabilization treatment).

The color developer used in the present invention contains:
Contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, typical examples include N,N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-
Amino-5-(N-ethyl-N-laurylamino)toluene, 4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline, 2-methyl-4-[N-ethyl-
N-(β-hydroxyethyl)amino]aniline, 4-
Amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-aniline, N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide, N,N-dimethyl-p- Phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline, 4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline, 4-amino-3-
Examples include methyl-N-ethyl-N-β-butoxyethylaniline. Particularly preferably 4-amino-
3-Methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-aniline. Also, these p
- The phenylenediamine derivative may be a salt such as a sulfate, a hydrochloride, a sulfite, or a p-toluenesulfonate. The amount of the aromatic primary amine developing agent used is preferably in a concentration of about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g per liter of developer solution.

[0065] In carrying out the present invention, in terms of the working environment,
Preferably, a developer solution containing substantially no benzyl alcohol is used. Here, “substantially not containing” means
Preferably 2 ml/liter or less, more preferably 0
．． A benzyl alcohol concentration of 5 ml/liter or less, and most preferably no benzyl alcohol at all.

In order to suppress fluctuations in photographic properties due to continuous processing, the color developer used in the present invention must be substantially free of sulfite ions (substantially free of sulfite ions herein means sulfite ion concentration). 3.0×10 −3 mol/liter or less) is more preferable. Most preferably, it does not contain any sulfite ions. However, in the present invention, a very small amount of sulfite ion used to prevent oxidation of the processing agent kit in which the developing agent is concentrated before being prepared into a solution for use is excluded.

The color developer used in the present invention preferably does not substantially contain sulfite ions, but may further contain substantially hydroxylamine in order to suppress fluctuations in photographic properties due to fluctuations in hydroxylamine concentration. It is more preferable that the hydroxylamine concentration is not more than 5.0×10 −3 mol/liter. Most preferably it does not contain any hydroxylamine.

The color developer used in the present invention preferably contains an organic preservative instead of the hydroxylamine or sulfite ion. The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. In other words, they are organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines,
Hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed rings Formula amines are particularly effective organic preservatives. These are Japanese Patent Publication No. 48-30496, Japanese Patent Publication No. 52
-143020, 63-4235, 63-30
No. 845, No. 63-21647, No. 63-44655
No. 63-53551, No. 63-43140, No. 63-56654, No. 63-58346, No. 63-
No. 43138, No. 63-146041, No. 63-44
No. 657, No. 63-44656, U.S. Patent No. 3,61
No. 5,503, No. 2,494,903, JP-A-1-9
No. 7953, No. 1-186939, No. 1-18694
No. 0, No. 1-187557, No. 2-306244, etc. As other preservatives, JP-A-57
-44148 and 57-53749, salicylic acids described in JP-A-59-180588, JP-A-63-239447, JP-A-63-128
No. 340, JP-A No. 1-186939 and JP-A No. 1-1875
Amines such as those described in No. 57, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
Aromatic polyhydroxy compounds described in No. 746,544 and the like may be used as necessary. In particular, alkanolamines such as triethanolamine, dialkylhydroxylamines such as N,N-diethylhydroxylamine and N,N-di(sulfoethyl)hydroxylamine, and hydrazines such as N,N-bis(carboxymethyl)hydrazine. It is preferable to add derivatives (excluding hydrazine) or aromatic polyhydroxy compounds typified by sodium catechol-3,5-disulfonate.

In particular, the use of dialkylhydroxylamine and/or hydrazine derivatives in combination with alkanolamines improves the stability of the color developer,
This is particularly preferred from the viewpoint of improving stability during continuous processing. In the present invention, chlorine ions are contained at 0.08 mol/liter or more for the purpose of suppressing fog and improving processing dependence. It is preferably contained in an amount of 0.09 to 0.5 mol/liter. Below this concentration, fogging tends to occur and processing dependence does not improve. Also, if the concentration is too high,
A decrease in maximum concentration occurs.

In the present invention, bromine ions are contained in the color developer at a concentration of 3.0×10 −5 mol/liter to 1.0×10 mol/liter.
-3 mol/liter is preferred. More preferably, it is 5.0 x 10-5 to 5 x 10-4 mol/liter. If the bromide ion concentration is more than 1 x 10-3 mol/liter, development will be delayed and the maximum density and sensitivity will be reduced; if it is less than 3.0 x 10-5 mol/liter, fog should be sufficiently prevented. I can't. Here, the chlorine ions and bromine ions may be added directly to the developer, or may be eluted from the photosensitive material into the developer during the development process.

When added directly to the color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, magnesium chloride, and calcium chloride. Alternatively, it may be supplied from an optical brightener added to the color developer.

Examples of the bromide ion supplying substance include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, and magnesium bromide. When eluted from the light-sensitive material during the development process, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion.

The color developer used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11. 0, and the color developer may contain other known developer component compounds. In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate,
Hydroxybenzoate, glycyl salt, N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1, 3
-Propanediol salts, valine salts, proline salts, trishydroxyaminomethane salts, lysine salts, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are soluble and have a high pH of 9.0 or higher.
It is particularly preferable to use these buffering agents because they have advantages such as excellent buffering ability in the area, no adverse effects on photographic performance (fogging, etc.) even when added to color developing solutions, and low cost.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, and sodium borate. , potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (
sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-2
-potassium hydroxybenzoate (potassium 5-sulfosalicylate), and the like.

The amount of the buffer added to the color developer is 0.
．． It is preferably 1 mol/liter or more, especially 0
．． Particularly preferred is 1 mol/liter to 0.4 mol/liter. In addition, various chelating agents can be used in the color developer to prevent precipitation of calcium or magnesium or to improve the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N
',N'-tetramethylene sulfonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid , 1-hydroxyethylidene-1,1-diphosphonic acid, N,N'-bis(2-
Examples include hydroxybenzyl)ethylenediamine-N,N'-diacetic acid and hydroxyethyliminodiacetic acid. Two or more of these chelating agents may be used in combination, if necessary. These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example, it is about 0.1 g to 10 g per liter.

[0076] Any development accelerator can be added to the color developer if necessary. As a development accelerator,
-16088, 37-5987, 38-782
6, No. 44-12380, No. 45-9019, and U.S. Pat. No. 3,813,247, etc.;
-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-1987-3
No. 0074, JP-A-56-156826 and JP-A No. 52-
Quaternary ammonium salts represented by No. 43429 etc., U.S. Patent Nos. 2,494,903 and 3,128,182
No. 4,230,796, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,482,
No. 546, No. 2,596,926 and No. 3,582,
Amine compounds described in No. 346 etc., Japanese Patent Publication No. 37-16
No. 088, No. 42-25201, U.S. Patent No. 3,12
No. 8,183, Special Publication No. 41-11431, No. 42-2
Polyalkylene oxides such as those disclosed in US Pat. No. 3,883 and US Pat. No. 3,532,501, 1-phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary. Benzyl alcohol is as described above.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

Color developers applicable to the present invention include:
Preferably, it contains an optical brightener. As the fluorescent brightener, 4,4'-diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 5 g/liter, preferably 0.1 g to 4 g/liter. Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, aromatic carboxylic acids, and polyalkylene imines may be added as necessary.

The processing temperature applied to the present invention is 36°C or higher, preferably 37°C to 45°C. If it is below the real temperature,
Sufficient color density cannot be obtained, and processing dependence also worsens. Further, the processing time of the present invention is 50 seconds or less, preferably 1
It is 0 seconds to 45 seconds. If the processing time exceeds this time, fogging tends to occur, which is not preferable. Although it is preferable that the amount of replenishment is small, it is suitably 20 to 600 ml, preferably 50 to 200 ml, and more preferably 60 to 150 ml per m2 of photosensitive material.

The photographic emulsion layer after color development is subjected to desilvering treatment. In the desilvering process, the bleaching process and the fixing process may be performed separately or simultaneously (bleach-fixing process). Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Furthermore, treatment in two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose.

Bleaching agents used in bleaching solutions and bleach-fixing solutions include, for example, iron salts; iron (III), cobalt (II),
I), compounds of polyvalent metals such as chromium (IV) and copper (II); peracids; quinones; nitro compounds and the like. Typical bleaching agents include iron chloride; ferricyanide; dichromate; organic complex salts of iron (III) (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropane). metal complex salts such as aminopolycarboxylic acids such as tetraacetic acid, glycol ether diamine tetraacetic acid, etc.); persulfates; bromates; permanganates;
Examples include nitrobenzenes. Among these, aminopolycarboxylic acid iron(III) complex salts, including ethylenediaminetetraacetate iron(III) complex salts and 1,3-diaminopropanetetraacetic acid iron(III) complex salts, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. . Additionally, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. Bleach solutions or bleach-fix solutions using these aminopolycarboxylic acid iron(III) complex salts are used at a pH of 3.0 to 8.

Known additives such as rehalogenating agents such as ammonium bromide and ammonium chloride; pH buffering agents such as ammonium nitrate; and metal corrosion inhibitors such as ammonium sulfate are added to the bleaching solution and bleach-fixing solution. be able to. Bleach and bleach-fix solutions contain, in addition to the above compounds,
It is preferable to contain an organic acid for the purpose of preventing bleach stains. Particularly preferred organic acids have acid dissociation constants (pk
Compounds in which a) is 2 to 5.5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but the use of thiosulfates are common, with ammonium thiosulfate being the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. As the preservative for the fixer and bleach-fixer, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294,769A are preferred. In addition, various aminopolycarboxylic acids and organic phosphonic acids (such as 1-hydroxyethylidene-1,1-diphosphonic acid, N,N,N',N' -ethylenediaminetetraphosphonic acid) is preferred.

The fixing solution and bleach-fixing solution can further contain various fluorescent brighteners; antifoaming agents; surfactants; polyvinylpyrrolidone; methanol and the like. bleach solution,
Bleach accelerators can be used in the bleach-fix solutions and their pre-baths, if necessary. Specific examples of useful bleach accelerators include U.S. Pat. No. 3,893,858, German Pat.
JP 53-32736, JP 53-57831, JP 53-37418, JP 53-72623, JP 53-
No. 95630, No. 53-95631, No. 53-104
No. 232, No. 53-124424, No. 53-1416
No. 23, No. 53-28426, Research Disclosure No. Compounds having a mercapto group or disulfide group as described in JP-A No. 17129 (July 1978); thiazolidine derivatives as described in JP-A-50-140129;
No. 32, No. 53-32735, U.S. Patent No. 3,706
, 561; West German Patent No. 1,1
No. 27,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748;
Polyoxyethylene compounds described in Japanese Patent Publication No. 430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others described in Japanese Patent Publication Nos. 49-42434, 49-59644, and 53
-94927, 54-35727, 55-26
Compounds described in No. 506 and No. 58-163940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, such as U.S. Pat.
The compound described in No. 0 is preferred. Additionally, U.S. Pat.
, 552,834 are also preferred. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes.
minutes, more preferably 20 seconds to 2 minutes. Further, the treatment temperature is 25°C to 50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate improves,
Moreover, the occurrence of stains after treatment is effectively prevented.

[0086] In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening stirring are disclosed in JP-A-62-183460 and JP-A-62-183.
461, a method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, a method of increasing the stirring effect using a rotating means as described in JP-A-62-183461, and a wiper blade provided in the liquid. Examples include a method of moving the light-sensitive material while bringing the emulsion surface into contact with the emulsion surface to create turbulent flow on the emulsion surface to further improve the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate. The agitation improvement means described above are more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect of the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is disclosed in Japanese Patent Application Laid-open Nos. 60-191257 and 60-19125.
It is preferable to have a photosensitive material conveying means described in No. 8 and No. 60-191259. The above-mentioned JP-A-60-1
As described in No. 91257, such a conveyance means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing performance deterioration of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The color light-sensitive material of the present invention is generally subjected to a water washing step after desilvering treatment. A stabilization process may be performed instead of the water washing process. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543, 58-14834,
All known methods described in No. 60-220345 can be used. Further, a washing step-stabilizing step may be carried out using a stabilizing bath containing a dye stabilizer and a surfactant as the final bath, as typified by the processing of color light-sensitive materials for photography. The washing liquid and stabilizing liquid include inorganic phosphoric acid,
Water softeners such as polyaminocargonic acids and organic aminophosphonic acids; metal salts such as Mg salts, Al salts, and Bi salts;
A surfactant; a hardening agent, etc. can be contained.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the material used, such as the coupler), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other factors. It can be set over a wide range depending on the conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society
Ty of Motion Picture and
Television Engineers Vol. 64, p. 248-253 (May 1955 issue). In addition, as a solution to problems such as bacterial growth and adhesion of generated floating substances to photosensitive materials, which occur when the amount of washing water is significantly reduced in the multistage countercurrent method, the method described in JP-A No. 62-288838 A method of reducing calcium ions and magnesium ions can be used very effectively. Also, JP-A-57-
Isothiazolone compounds and thiabendazoles described in No. 8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi.
"Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Hygiene Technology Association "Sterilization, Disinfection, and Antifungal Technology of Microorganisms" (1982)
“Encyclopedia of Antibacterial and Antifungal Agents” edited by the Society of Industrial Engineers and the Japan Society of Antibacterial and Antifungal Agents (
It is also possible to use the fungicides described in (1986).

The pH of the washing water is 4-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is 15 to 45°C.
for 20 seconds to 10 minutes, preferably for 30 seconds to 25 to 40°C.
A range of 5 minutes is selected. Examples of the dye stabilizer that can be used in the stabilizing liquid include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. In addition, the stabilizing liquid includes other pH adjusting buffers such as boric acid and sodium hydroxide;
1-Hydroxyethylidene-1,1-diphosphonic acid; a chelating agent such as ethylenediaminetetraacetic acid; an antisulfurizing agent such as alkanolamine; a fluorescent whitening agent; an antifungal agent, etc. can be contained.

[0091] The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other processes such as the desilvering process. When each of the above processing solutions becomes concentrated due to evaporation during processing using an automatic processor, etc.,
It is preferable to correct the concentration by adding water.

The color photographic material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing, and it is preferable to use various precursors of the color developing agent. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, U.S. Pat. No. 3,342,59
No. 9, RD magazine No. No. 14850 and the same No. 1515
The Schiff base type compound described in No. 9, the Schiff base type compound described in No. 9; 13924
Aldol compounds described in US Pat. No. 3,719,4
Examples include the metal salt complexes described in No. 92 and the urethane compounds described in JP-A-53-135628.

The color photosensitive material of the present invention may contain various types of 1-phenyl-3, if necessary, for the purpose of promoting color development.
- Pyrazolidones may be incorporated. Typical compounds are JP-A-56-64339, JP-A-57-144547,
and No. 58-115438.

[0094]

[Examples] The present invention will be explained in detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 After corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin undercoat layer containing sodium dodecylbenzene sulfonate was applied, and various photographic constituent layers were further coated. Multilayer color photographic paper A having the layer structure shown below was produced. The coating solution was prepared as follows.

Preparation of fifth layer coating solution: 32.0 g of cyan coupler (ExC), color image stabilizer (C
pd-2) 3.0g, color image stabilizer (Cpd-4) 2.0
g, color image stabilizer (Cpd-6) 18.0 g, color image stabilizer (Cpd-7) 40.0 g, and color image stabilizer (Cpd-8)
), 50.0 cc of ethyl acetate and solvent (So
lv-6) was added and dissolved, and this solution was added to 500 cc of a 20% gelatin aqueous solution containing 8 cc of sodium dodecylbenzenesulfonate, and then emulsified and dispersed using an ultrasonic homogenizer to prepare an emulsified dispersion. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.58
A 1:4 mixture (Ag molar ratio) of a large size emulsion of μm and a small size emulsion of 0.45 μm. The coefficient of variation of grain size distribution is 0.09 and 0.11, respectively, and each size emulsion is A.
A particle containing 0.6 mol % of gBr locally on a part of the particle surface was prepared. This emulsion contains red-sensitive sensitizing dye E shown below at 0.9x per mole of silver for large size emulsions.
10-4 mol, or 1.1 x 1 for small size emulsions
0-4 mol is added. Further, chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a fifth layer coating solution having the composition shown below.

Coating solutions for the first to fourth, sixth and seventh layers were also prepared in the same manner as the fifth layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, the total amount of Cpd-10 and Cpd-11 was 25% each in each layer.
．． It was added at a concentration of 0 mg/m2 and 50.0 mg/m2. The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each light-sensitive emulsion layer.

[Blue-sensitive emulsion layer] Sensitizing dye A

[C25] and sensitizing dye B

[Formula 26] (2.0 x 10-4 mol each for large size emulsions and 2.5 x 10-4 mol each for small size emulsions per 1 mol silver halide)

[Green-sensitive emulsion layer] Sensitizing dye C

[Formula 27] (per mole of silver halide, 4.0 x 10-4 mole for large size emulsion, 5.6 mole for small size emulsion)
x 10-4 mol) and sensitizing dye D

[Chemical formula 28] (per mole of silver halide, 7.0 x 10-5 mole for large size emulsions, and 1 mole for small size emulsions)
．． 0x10-5 mol)

[Red-sensitive emulsion layer] Sensitizing dye E

[Formula 29] (0.9 x 10-4 mol per mol of silver halide for large size emulsions, and 1 mol for small size emulsions)
．． 1 x 10-4 mol)

Furthermore, the following compound was added in an amount of 2.6×10 −3 mol per mol of silver halide.

[0102]

[C30]

Furthermore, 1-(5-methylureidophenyl) was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer.
-5-mercaptotetrazole at 8.5 x 10-5 mol and 7.7 x 10-4 mol per mol of silver halide, respectively.
mol, 2.5×10 −4 mol was added. In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added at 1 x 10-4 mol and 2 mol per mol of silver halide, respectively. ×1
0-4 mol was added. In addition, in order to prevent irradiation, the following dyes are added to the emulsion layer (the amount in parentheses indicates the coating amount).
was added.

[0104]

[Chemical formula 31]

(Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m2). Silver halide emulsions represent coating amounts in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO2) and a bluish dye (ulmarine blue)]

[
First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average grain size 0.88 μm)
A 3:7 mixture (silver molar ratio) of a large size emulsion of
Each size emulsion contains 0.3 mol% silver bromide locally on a part of the grain surface) 0.30 Gelatin

1.86 Yellow coupler (ExY)

0.82 Color image stabilizer (Cpd-1)

0.19 Solvent (Solv-3)

0.18 Solvent (Solv-7)

0.18 Color image stabilizer (C
pd-7)
0.06

0108 Second layer (color mixing prevention layer) Gelatin

0.99 Color mixing prevention agent (Cpd-5)

0.08 Solvent (Solv-1)

0.16 Solvent
-4)
0.08

0109
]Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average grain size 0.55μ
A 1:3 mixture of a large size emulsion of 0.39μ and a small size emulsion of 0.39μ (Ag molar ratio). The coefficient of variation of particle size distribution is 0.10 and 0.08, respectively.
, each size emulsion contained 0.8 mol% of AgBr locally on a part of the grain surface)
0.12 Gelatin

1.24 Magenta coupler (
ExM)
0.23 Color image stabilizer (Cp
d-2)
0.03 Color image stabilizer (
Cpd-3)
0.16 Color image stabilizer (Cpd-4)
0.02 Color image stabilizer (Cpd-9)
0.02
Solvent (Solv-2)
0.
40

[0110] Fourth layer (ultraviolet absorbing layer) Gelatin

1.58 Ultraviolet absorber (UV-1)

0.47 Color mixing inhibitor (Cpd-5
)
0.05 Solvent (Solv-5
)
0.24

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average grain size 0.58 μm)
A 1:4 mixture of a large size emulsion of 0.45μ and a small size emulsion of 0.45μ (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, and each size emulsion contained 0.6 mol% of AgBr locally on a part of the grain surface) 0.23
gelatin

1.34 Cyan coupler (ExC)

0.32 Color image stabilizer (Cpd-2
)
0.03 Color image stabilizer (Cpd
-4)
0.02 Color image stabilizer (C
pd-6)
0.18 Color image stabilizer (Cpd-7)
0.40 Color image stabilizer (Cpd-8)
0.05 Solvent (Solv-6)
0.1
4

[0112] Sixth layer (ultraviolet absorbing layer) Gelatin

0.53 Ultraviolet absorber (UV-1)

0.16 Color mixing inhibitor (Cpd-5
)
0.02 Solvent (Solv-5
)
0.08

0113
] Seventh layer (protective layer) Gelatin

1.33 Acrylic modified copolymer of polyvinyl alcohol
(denaturation degree 17%)

0.17 Liquid paraffin
0.03

[
[0114]

[C32]

[0115]

[Chemical formula 33]

[0116]

[C34]

[0117]

[C35]

[0118]

[C36]

[0119]

[C37]

[0120]

[C38]

[0121]

[C39]

[0122]

[C40]

Next, change the yellow coupler ExY of photographic paper A to the following yellow coupler to prepare photographic paper B, C, D,
E and F were produced.

[0124]

[C41]

[0125] Photographic paper D Y-1 Photographic paper E Y-5 Photographic paper F Y-12

The photographic papers A to F obtained as described above were exposed to light at 250 CMS through a wedge-shaped wedge and processed in the following processing steps.

Treatment process temperature
Time (seconds) Color development 39℃
45 bleach fixing 30-35℃
45 Rinse■ 30-35℃
20 rinse■ 30-35℃
20 rinse■ 30-35℃
20 rinse■ 30-35℃
30 The composition of each treatment liquid is as follows.

[Color developer]

tank liquid water

800ml EDT
A・2Na

3g sodium catechol-3,5-disulfonate 0.3g triethanolamine
8.0g
potassium bromide

0.03g sodium chloride

See Table 1 N,N-di(sulfoethyl)hydroxylamine
5.0g Fluorescent brightener (WHITEX 4
, manufactured by Sumitomo Chemical) 1.
0g Sodium triisopropylnaphthalene-β-sulfonate 0.3g N-ethyl-N-
(β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate
Add 5.0g water

1000ml pH
(25℃)
10.
05

Bleach-fixing tank liquid water

800ml ammonium thiosulfate (50% by weight)
120ml ammonium sulfite

17g ethylenediaminetetraacetic acid iron(III) ammonium
60g ethylenediaminetetraacetic acid/2Na
3g glacial acetic acid


Add 7g water

1000ml pH (25℃)

5.50

0130
] Rinse solution ion exchange water (3 ppm each of calcium and magnesium
below)

Table 6 shows the sodium chloride concentration of the color developer.
, as shown in Table 7, and further adjusted the pH to around 10
．． Tables 6 and 7 show the amount of change in yellow Dmin and Dmax from the standard pH at each sodium chloride concentration.

[0132]

[Table 6]

[0133]

[Table 7]

With the chloride ion concentration of the present invention, when the yellow coupler of the present invention is used, the Dm
The decrease in ax is small, and the increase in Dmin due to pH increase
There is also a small increase in processing dependence, which significantly improves processing dependence.

Example 2 Instead of yellow coupler Y-1 of photographic paper D in Example 1, Y-2, Y-4, Y-13, Y-20, Y-25, Y
-27 was used in the same manner as in Example 1, and excellent pH dependence was obtained at the chloride ion concentration of the present invention.

Example 3 Chlorine ion concentration 0.06 shown in Example 1, Tables 6 and 7
Two color developers of mol/liter and 0.30 mol/liter were used, and the processing temperatures were 35°C and 38°C, respectively.
In addition, the treatment times were set to 30 seconds and 60 seconds, and the samples A and D used in Example 1 were treated under these conditions. As in Example 1, the amount of change in Dmin and Dmax with respect to pH change is shown. The results are shown in Table 8.

[0137]

[Table 8]

As described above, according to the present invention, it was possible to obtain photographic characteristics that were extremely stable against pH changes.

Example 4 Same as Example 3, but instead of pH change,
Table 9 shows the changes in photographic properties when the color developing agent (N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate) was varied by ±1.5 g.

[0140]

[Table 9]

According to the present invention, even if the color developing agent concentration was changed, the photographic properties did not change, and stable performance could be obtained.

[0142]

[Effects of the Invention] According to the method for processing silver halide color photographic materials of the present invention, there is little fog in rapid processing, sufficient color development is obtained, and fluctuations in photographic properties are significantly reduced. It has excellent effects.

Claims (2)

[Claims] Claim 1: A silver halide color photographic light-sensitive material containing at least one acylacetamide type yellow coupler having an acyl group represented by the following general formula (I) is heated for 50 seconds or less at 36°C or higher to reduce the chloride ion concentration. 1. A method for processing a silver halide color photographic material, which comprises developing with a developer having a concentration of 0.08 mol/liter or more. General formula (I) [Formula 1] (In the formula, R1 represents a monovalent group, Q together with C
-Represents a group of nonmetallic atoms necessary to form a 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle having at least one heteroatom selected from N, S, O, and P in the ring. However, R1 is not a hydrogen atom and does not combine with Q to form a ring. ) Claim 2: The silver halide color photographic material comprises:
2. The method for processing a silver halide color photographic material according to claim 1, wherein at least one layer contains a high silver chloride emulsion containing 90 mol % or more of silver chloride.