JPH11119400A - Processing of silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make obtainable a color image which is stable for a long time without increase in dye image density with time after development even when the processing time for development is reduced. SOLUTION: At least one layer of a cyan developing red-sensitive silver halide emulsion layer in the silver halide color photographic sensitive material contains a pyrrolotriazole-type cyan coupler. The photosensitive material is exposed, developed, desilverized, washed with water and/or stabilized, then directly heated with a heat roller, and dried by blowing with hot air of >=1000 kg/m<2> .hr mass velocity through a perforated plate or nozzles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material (hereinafter, also simply referred to as a "light-sensitive material"). The present invention relates to a processing method for obtaining a color print.

[0002]

2. Description of the Related Art In general, in a processing method of a silver halide photographic light-sensitive material, color development, desilvering, washing and / or stabilization are performed. At present, the most popular image recording method, the negative / paper method, is to load a color negative film into a camera, take a picture, develop it, and print and develop it on color photographic paper (also called color paper). This is a method of obtaining an image (also called a print).

In recent years, in the field of color photographic processing, technology development for digitizing image information to improve finished quality, simplify and improve the accuracy of work processes, and expand the range of application has been progressing. For example, FRONTIER Digital photo printers that combine silver halide photography and digital technology, such as With the development of digital photo printers, as the speed of digital image processing, which previously required time in the printer unit, has been increasing, there has been a strong demand for faster development processing in the processor unit. I have. However, in the past, many studies have been made on speeding up the immersion processing step of the development processing, and remarkable speeding up has been performed. Therefore, there is a strong demand for speeding up of the drying step following the immersion processing step. But,
When the drying process is accelerated, there is a phenomenon that the image density changes over time during storage of the print after the development processing, specifically, the phenomenon that the cyan dye density increases over time, and the stable storage of the color print image It is not preferable from the viewpoint of sex.

Regarding this drawback, in an image recording medium such as a color negative film, by combining digital image processing, the ability to improve a finished image by controlling an image quality factor, which is an advantage thereof, is utilized, and extremely rapid processing including omission and shortening of steps is achieved. By performing development, it is possible to correct and remedy the deterioration of image storability and the deterioration of image quality by image processing. In other words, it is possible to perform image processing to obtain high-quality prints even if the photographic properties change due to improper development processing or aging after the development processing. JP-A-6-123926,
Nos. 7-020585 and 9-102874. On the other hand, color print is the final image medium to which digital image processing is sometimes added as indicated by the name of color hard copy from the viewpoint of use, so the photographic properties over time after development processing It has been particularly strongly desired that there be no change, in particular no increase in cyan dye image density.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to maintain a sufficient image quality even in a process in which the processing time, especially the drying time, is reduced, and to increase the cyan image density over time after the development process. It is an object of the present invention to provide a processing method for obtaining a color print having a stable image for a long period without any problem.

[0006]

The inventor of the present invention uses a specific coupler for a color photographic light-sensitive material and, under the specific drying conditions during the development processing, can shorten the drying step. It has been found that the increase in photographic density of the obtained image with time is suppressed, and as a result of earnest studies based on this new fact, the present invention has been reached. That is, the present invention has the following configurations.

[0007] 1. After exposing a silver halide color photographic light-sensitive material having at least a cyan-color-forming photosensitive silver halide emulsion layer and a non-color-forming and non-photosensitive hydrophilic colloid layer on a support, color development, desilvering, washing with water and / Or stabilization, and in the processing method of sequentially performing the processing of each step of drying,
(1) At least one of the cyan-color-forming photosensitive silver halide emulsion layers contains at least one cyan dye-forming coupler selected from the compounds represented by the following formula (I); After the photosensitive material is contact-heated by a heat roller in the drying step, the photosensitive material is blown dry by warm air blown from the perforated plate or the nozzle group toward the photosensitive material, and (3) in the blow drying, the photosensitive material is dried. Wherein the mass velocity of warm air blown per unit area of the heat receiving surface is 1000 kg / m ² · hr or more.

[0008]

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[0009] In formula ^{(I), Z a, Z} b each represents -C
(R ³ ) = or -N =. However Z ^a, one of Z ^b is -N =, the other is -C (R ³⁾ is =.
R ¹ and R ² are Hammett's substituent constant σ _p
Represents an electron withdrawing group having a value of 0.20 or more, and R ¹ and R ²
The sum of the sigma _p value is 0.65 or more. R ³ represents a hydrogen atom or a substituent. X represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of a color developing agent. The group of R ¹ , R ² , R ^3, or X may be a divalent group and form a homopolymer or a copolymer by combining with a dimer or higher polymer or a polymer chain.

[0010] 2. A silver halide color photographic light-sensitive material contains a compound represented by the following general formula (III) in one or both of a cyan-sensitive photosensitive silver halide emulsion layer and a non-color-forming and non-photosensitive hydrophilic colloid layer. 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, comprising at least one kind.

[0011]

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In the formula (III), R ^a1 and R ^a2 each independently represent
Represents a hydrogen atom, an alkyl group or an aryl group. R
^a3 and ^Ra4 represent a hydrogen atom, an alkyl group or an aryl group. R ^a5 represents an aryl group. However, ^Ra1 , ^Ra2
, R ^a3 , R ^a4 and R ^a5 do not total 13 or less.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. As described above, the present invention provides a silver halide containing a cyan dye-forming coupler having a specific structure represented by the general formula (I) (hereinafter also referred to as a cyan coupler) and preferably a specific compound represented by the general formula (III) It consists of using a color photographic light-sensitive material (hereinafter also referred to as a color light-sensitive material) and adopting specific drying conditions during its development. As described above, many color-developed photosensitive materials have a problem that the image density changes during the subsequent aging, and it is particularly difficult to set an optimum finish because the density of the cyan dye image increases. A photosensitive material using a pyrrolotriazole type cyan coupler represented by the general formula (I) is no exception. However, in the development process, a method is used in which high-temperature air blown from a nozzle or a perforated plate is directly blown onto the surface of the photosensitive material after the photosensitive material is dried by contact heating as described above, and the mass flow rate is 1000 kg. / M ² · hr or more, the above-mentioned increase in image density over time is prevented, and a stable image is obtained. The use of a pyrrolotriazole type cyan coupler in the light-sensitive material, and directly applying the airflow of the above-mentioned air volume to the surface of the light-sensitive material in the drying step during the development processing are the key points of the present invention, and the object of the present invention is thereby achieved. The effect to be obtained is obtained. Therefore, it is necessary to describe both the photosensitive material and the development processing step in order to sufficiently show the configuration contents and embodiments of the present invention, and the description will be made in the following order.

1. First, the cyan dye-forming coupler represented by formula (I) and the specific compound represented by formula (III) according to the present invention will be described. 2. Further, the color photographic material according to the present invention will be supplementarily explained except for the coupler of the general formula (I) and the compound of the general formula (III). 3. Next, the developing process and the processing apparatus according to the present invention will be described in accordance with an actual example of the developing apparatus, particularly focusing on the drying step. 4. A supplementary explanation will be given on the development processing step and processing method according to the present invention.

[0015] First, described cyan coupler of formula (I) used in the color light-sensitive material of the present invention, slightly supplement the Hammett's substituent constant sigma _p value in the description of the substituents in the structure formula . The Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of a benzene derivative, and is widely accepted today. The substituent constant determined by Hammett's rule is σ
There is _p value and sigma _m value and these values can be found in many general books, for example, JADean ed, "Lang
e's Handbook of Chemistry, 12th edition, 1979 (Mc Graw-Hill)
See pages 6-103, 1979 (Nankodo). In addition,
In the present invention, each substituent is defined or described by Hammett's substituent constant σ _p, but this is found in the above-mentioned textbook, in the sense that it is limited only to a substituent having a known value in the literature. In addition, it goes without saying that even if the value is unknown in the literature, it also includes a substituent that will be included in the range when measured based on the Hammett rule. Although the compound represented by the general formula (I) of the present invention is not a benzene derivative, the σ _p value is used as a measure of the electronic effect of the substituent regardless of the substitution position. In the present invention, the σ _p value will be used in this sense in the future. The term “lipophilic” as used in the present invention means that the solubility in water at room temperature is 1%.
It is less than 0%.

In the present specification, the term "aliphatic" means a straight or branched chain, which may be saturated or unsaturated, and further includes a cyclic one. Represents alkenyl, alkynyl, cycloalkyl, or cycloalkenyl, which may further have a substituent. In addition, aromatic represents aryl, which may further have a substituent. Heterocycle (heterocycle) has a heteroatom in the ring, and also includes an aromatic group. And may further have a substituent. The substituents in the present specification and the substituents that may be present on these aliphatic, aromatic and heterocyclic rings may be any groups that can be substituted unless otherwise specified, and include, for example, aliphatic groups and aromatic groups. Group, heterocyclic group, acyl group, acyloxy group, acylamino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, aliphatic Carbamoyl group, aromatic carbamoyl group, aliphatic sulfonyl group, aromatic sulfonyl group, aliphatic flufamoyl group, aromatic sulfamoyl group, aliphatic sulfonamide group, aromatic sulfonamide group, aliphatic amino group, aromatic amino group, Aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic thio group, aromatic thio group, mercapto group, hydroxy group, cyano group, nitro Group, hydroxyamino group,
Examples include a halogen atom.

Next, the system represented by the general formula (I) of the present invention will be described.
The uncoupler will be described in detail. Z^aAnd Z^bHaso
Each -C (R^Three) = Or -N =. Where Z^aPassing
And Z^b Is -N = and the other is -C (R^Three)
=.

R ³ represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group. Group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxy Carbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group,
Examples include a phosphonyl group, an aryloxycarbonyl group, and an acyl group. These groups may be further substituted with substituents as exemplified for R ³ .

More specifically, R ³ is a hydrogen atom, a halogen atom (for example, a chlorine atom or a bromine atom), an alkyl group (for example, a linear or branched alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group). Group, alkynyl group, cycloalkyl group, cycloalkenyl group, specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecaneamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl group (for example, phenyl, 4-t-butylphenyl, 2,4-di-t-amyl) Phenyl, 4-tetradecanamidophenyl), a heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl,
2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy,
2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t
-Butylphenoxy, 3-nitrophenoxy, 3-t-
Butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (for example, acetamido, benzamido, tetradecanamido, 2- (2,4
-Di-t-amylphenoxy) butanamide, 4- (3
-T-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl)
Phenoxy didecaneamide), alkylamino groups (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino),

Further, anilino groups (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro- 5- {2- (3-t-butyl-4-hydroxyphenoxy) dodecaneamide} anilino), a ureido group (eg, phenylureido, methylureide, N, N-dibutylureido), a sulfamoylamino group (eg,
N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-
Tetradecanamidophenylthio), an alkoxycarbonylamino group (eg, methoxycarbonylamino, tetradecyloxycarbonylamino), a sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfone) Amide, 2-methoxy-5-t-butylbenzenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N
-Dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), a sulfamoyl group (for example, , N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl Groups (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl groups (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy groups (eg,
1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo) , An acyloxy group (eg, acetoxy),
A carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), an aryloxycarbonylamino group (eg, phenoxycarbonylamino), an imide group (eg, , N-succinimide, N-phthalimide,
3-octadecenylsuccinimide), a heterocyclic thio group (eg, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-
Pyridylthio), a sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl,
3-phenoxypropylsulfinyl), a phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl), an acyl group (eg, acetyl, 3-phenylpropanoyl) Benzoyl, 4-dodecyloxybenzoyl).

R ³ is preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, or an alkoxycarbonylamino group. , Sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl group Can be mentioned.

More preferably, they are an alkyl group or an aryl group, more preferably an alkyl group or an aryl group having at least one substituent, and further preferably, at least one alkyl group or an alkoxy group from the viewpoint of cohesiveness. , A sulfonyl group, a sulfamoyl group, a carbamoyl group, an acylamide group or an alkyl group or an aryl group having a sulfonamide group as a substituent. Particularly preferred is an alkyl group or an aryl group having at least one alkyl group, acylamide group or sulfonamide group as a substituent. When these substituents are present in the aryl group, it is more preferable to have them at least in the ortho or para position.

The cyan coupler of the present invention, wherein R ¹ and R ² are both 0.20 or more electron-withdrawing group, and R ¹
The sum of sigma _p values of R ² are those which develops as a cyan image by 0.65 or more. The sum of the σ _p values of R ¹ and R ² is preferably 0.70 or more, and the upper limit is about 2.0.

R ¹ and R ² are Hammett's substituent constant σ _p
An electron-withdrawing group having a value of 0.20 or more. Preferably,
It is an electron-withdrawing group of 0.30 or more. The upper limit is 1.
It is an electron-withdrawing group of 0 or less.

Specific examples of the electron-withdrawing groups R ¹ and R ^{2 having} a σ _p value of 0.20 or more include an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group , a halogenated alkyl group, halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group which sigma _p value is substituted with 0.20 or more other electron-withdrawing group, Heterocyclic group, halogen atom, azo group, or Renoshianeto group, and the like. Among these substituents, the group which can have a substituent may further have a substituent as described for R ³ .

[0026] Further details the R ¹ and R ^2, σ _p
Examples of the electron-withdrawing group having a value of 0.20 or more include an acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), an acyloxy group (eg, acetoxy), a carbamoyl group (eg, carbamoyl) , N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dibutylcarbamoyl, N
-(2-dodecyloxyethyl) carbamoyl, N-
(4-n-pentadecanamido) phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3
-(2,4-di-t-amylphenoxy) propyl} carbamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, iso-propyloxycarbonyl, tert-butyloxycarbonyl, iso-
Butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), cyano group, nitro group, dialkylphosphono group (eg, dimethylphosphono), diarylphosphono group (E.g., diphenylphosphono), diarylphosphinyl group (e.g., diphenylphosphinyl), alkylsulfinyl group (e.g., 3-phenoxypropylsulfinyl), arylsulfinyl group (e.g.,
3-pentadecylphenylsulfinyl), alkylsulfonyl group (eg, methanesulfonyl, octanesulfonyl), arylsulfonyl group (eg, benzenesulfonyl, toluenesulfonyl), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy), acylthio Groups (eg, acetylthio, benzoylthio), sulfamoyl groups (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-
(2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), thiocyanate group, thiocarbonyl group (eg, methylthiocarbonyl, phenylthiocarbonyl), alkyl halide Groups (eg, trifluoromethane, heptafluoropropane), halogenated alkoxy groups (eg, trifluoromethyloxy), halogenated aryloxy groups (eg, pentafluorophenyloxy), halogenated alkylamino groups (eg, N, N-
Di- (trifluoromethyl) amino), a halogenated alkylthio group (for example, difluoromethylthio, 1,1,2,2
2-tetrafluoroethane ethylthiomethyl), an aryl group substituted with sigma _p 0.20 or more other electron withdrawing group (e.g., 2,
4-dinitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl), a heterocyclic group (for example, 2-
Benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1-pyrrolyl), halogen atom (eg, chlorine atom, bromine atom), azo group (eg, phenylazo)
Or a selenocyanate group. Among these substituents, the group which can have a substituent may further have a substituent as described for R ³ .

R ¹ and R ² are preferably acyl, acyloxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfinyl, arylsulfinyl, Alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, halogenated alkyl group, halogenated alkyloxy group, halogenated alkylthio group,
A halogenated aryloxy group, two or more σ _p 0.20
An aryl group substituted with the other electron-withdrawing group and a heterocyclic group can be exemplified. More preferred are an alkoxycarbonyl group, a nitro group, a cyano group, an arylsulfonyl group, a carbamoyl group and a halogenated alkyl group. Most preferred as R ¹ is a cyano group. Particularly preferred as R ² is an alkoxycarbonyl group, and most preferred is a branched alkoxycarbonyl group (especially a cycloalkoxycarbonyl group).

X represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized product of a color developing agent. Or arylsulfonyloxy group, acylamino group, alkyl or arylsulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, carbamoyloxy group, heterocyclic carbonyloxy group, There are a 5- or 6-membered nitrogen-containing heterocyclic group, an imide group, an arylazo group and the like, and these groups may be further substituted with a group permitted as a substituent of R ³ . Examples of the color developing agent which is an oxidized form of the color developing agent include hydrazine developing agents such as carbamoylhydrazine developing agents and sulfamoylhydrazine developing agents in addition to known aromatic primary amine color developing agents. Can be mentioned. Preferred are aromatic primary amine color developing agents.

More specifically, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkoxy group (for example, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methanesulfonylethoxy, ethoxycarbonylmethoxy), aryl An oxy group (e.g., 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarbonylphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (eg, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl Sulfonyloxy group (for example, methanesulfonyloxy, toluenesulfonyloxy), acylamino group (for example, dichloroacetylamino, heptafluorobutyrylamino), alkyl or arylsulfonamide group (for example, methanesulfonylamino,
Trifluoromethanesulfonylamino, p-toluenesulfonylamino), alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy), alkyl,
Aryl or heterocyclic thio groups (e.g. dodecylthio, 1-carboxydodecylthio, phenylthio, 2-
Butoxy-5-t-octylphenylthio, tetrazolylthio), carbamoylamino group (eg, N-methylcarbamoylamino, N-phenylcarbamoylamino), carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, N-ethylcarbamoyl) Oxy, N-ethyl-N-phenylcarbamoyloxy),
Heterocyclic carbonyloxy group (eg, morpholinocarbonyloxy, piperidinocarbonyloxy), 5- or 6-membered nitrogen-containing heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2
-Dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, phenylazo, 4-methoxyphenylazo) and the like. X is an aldehyde or ketone as a leaving group bonded via a carbon atom.
It may take the form of a bis-type coupler obtained by condensing an equivalent coupler. X may contain a photographically useful group such as a development inhibitor and a development accelerator.

Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, an alkyloxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a heterocyclic carbonyloxy group, or a nitrogen atom at the coupling active site. A 5- or 6-membered nitrogen-containing heterocyclic group bonded by an atom. More preferred X is a halogen atom, an alkyl or arylthio group, an alkyloxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a heterocyclic carbonyloxy group, and particularly preferred are a carbamoyloxy group and a heterocyclic carbonyloxy group. It is.

In the cyan coupler represented by the general formula (I), the group represented by R ¹ , R ² , R ³ or X becomes a divalent group, and binds to a dimer or higher polymer or a polymer chain. To form a homopolymer or a copolymer. A typical example of the homopolymer or copolymer bonded to a polymer chain is an addition polymer having a cyan coupler residue represented by the general formula (I), a homopolymer or a copolymer of an ethylenically unsaturated compound. . In this case, the polymer may contain one or more cyan coloring repeating units having a cyan coupler residue represented by the general formula (I), and one of the non-coloring ethylene type monomers as a copolymerization component. It may be a copolymer containing one or more species. The cyan coloring repeating unit having a cyan coupler residue represented by the general formula (I) is preferably represented by the following general formula (P).

[0032]

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In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and A represents -CONH-, -COO-
Or a substituted or unsubstituted phenylene group, B represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, and L represents -CONH-, -NHCONH-,
-NHCOO-, -NHCO-, -OCONH-, -NH-, -COO
-, - OCO -, - CO -, - O -, - S -, - SO 2 -, -
It represents NHSO ₂ — or —SO ₂ NH—. a, b, and c represent 0 or 1. Q is R of the compound represented by the general formula (I)
¹ , represents a cyan coupler residue from which a hydrogen atom has been removed from R ² , R ³ or X. As the polymer, a copolymer of a cyan-color-forming monomer represented by a coupler unit of the general formula (I) and a non-color-forming ethylene-like monomer that does not couple with an oxidation product of a developing agent is preferable.

The non-color-forming ethylenic monomer which does not couple with the oxidation product of the developing agent includes acrylic acid, α-
Chloroacrylic acid, α-alkylacrylic acid (eg, methacrylic acid) Amides or esters derived from these acrylic acids (eg, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methyl acrylate) , Ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β- Hydroxy methacrylate), vinyl esters (eg, vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile , Methacrylonitrile, aromatic vinyl compounds (eg, styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg, vinyl ethyl ether) ), Maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylilipyridine and 2- and -4-vinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. The non-color-forming ethylene type monomer used here can be used in combination of two or more kinds. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, and methyl acrylate and diacetone acrylamide can be used.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinylic monomer corresponding to the above general formula (I) is used to form the copolymer having physical properties and / or Alternatively, it can be selected such that the chemical properties, eg, solubility, compatibility with the binder of the photographic colloid composition, eg, gelatin, its flexibility, thermal stability, etc., are favorably affected.

The silver halide light-sensitive material of the cyan coupler of the present invention, the preferably to be contained in the red-sensitive silver halide emulsion layer, it is preferable to so-called internal type coupler. For this purpose, R ^1, R ² , at least one of R ³ and X is a so-called ballast group (preferably having a total carbon number of 1).
0 or more), and more preferably 10 to 50 carbon atoms in total. Particularly, it is preferable that R ³ has a ballast group. The cyan coupler represented by the general formula (I) is more preferably a compound having a structure represented by the following general formula (II).

[0038]

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In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different and each represents a hydrogen atom or a substituent. As the substituent, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aryl group is preferable, and more preferable ones are described below. R ¹¹ and R ^{12 each} preferably represent an aliphatic group, for example, a linear, branched or cyclic alkyl group, aralkyl group, alkenyl group, alkynyl group or cycloalkenyl group having 1 to 36 carbon atoms. For example, methyl, ethyl, propyl, isopropyl, t-butyl, t
-Represents amyl, t-octyl, tridecyl, cyclopentyl, cyclohexyl. The aliphatic group more preferably has 1 to 12 carbon atoms. R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom or an aliphatic group. Examples of the aliphatic group include the groups described above for R ¹¹ and R ¹² . R ¹³ , R ¹⁴ , R
¹⁵ is particularly preferably a hydrogen atom.

Z is necessary for forming a 5- to 8-membered ring,
Represents a group of non-metallic atoms, and this ring may be substituted, may be a saturated ring or may have an unsaturated bond.
Preferred non-metallic atoms include a nitrogen atom, an oxygen atom, a sulfur atom and a carbon atom, and more preferably a carbon atom. Examples of the ring formed by Z include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring,
Cyclooctane ring, cyclohexene ring, piperazine ring,
Examples thereof include an oxane ring and a thiane ring, and these rings may be substituted with a substituent represented by R ³ described above. Preferably the ring formed by Z is a cyclohexane ring which may be substituted, especially preferably, 4-position substituted with a substituent as represented by an alkyl group (the aforementioned R ³ having 1 to 24 carbon atoms A cyclohexane ring substituted with

[0041] formula R ³ of (II) has the same meaning as R ³ of formula (I), particularly preferably an alkyl group or an aryl group, more preferably a substituted aryl group. From the viewpoint of the number of carbon atoms, in the case of an alkyl group, preferably 1
To 36, and in the case of an aryl group, preferably 6
~ 36. Among the aryl groups, those in which the alkoxy group is substituted at the ortho position of the bond position to the coupler mother nucleus are not preferred because the light fastness of the dye derived from the coupler is low. In that respect, the substituent of the aryl group is preferably a substituted or unsubstituted alkyl group, and among them, an unsubstituted alkyl group is most preferred. Particularly, an unsubstituted alkyl group having 1 to 30 carbon atoms is preferable.

X ² represents a hydrogen atom or a substituent. The substituent is X ² -C (=
O) Groups which promote the elimination of the O- group are preferred. X ² is preferably a heterocyclic ring, a substituted or unsubstituted amino group, or an aryl group. The hetero ring is preferably a 5- to 8-membered ring having a nitrogen atom, an oxygen atom, or a sulfur atom and having 1 to 36 carbon atoms. More preferably,
A 5- or 6-membered ring bonded by a nitrogen atom, of which a 6-membered ring is particularly preferred. These rings may form a condensed ring with a benzene ring or a hetero ring. Specific examples include imidazole, pyrazole, triazole, lactam compounds, piperidine, pyrrolidine, pyrrole, morpholine,
Pyrazolidine, thiazolidine, pyrazoline and the like, preferably, morpholine, piperidine,
Particularly, morpholine is preferred. Examples of the substituent of the substituted amino group include an aliphatic group, an aryl group and a heterocyclic group. Examples of the aliphatic group include the substituents of R ^{3 described} above, and further include a cyano group, an alkoxy group (eg, methoxy), an alkoxycarbonyl group (eg, ethoxycarbonyl), a chlorine atom, a hydroxyl group, a carboxyl group, and the like. May be substituted. As the substituted amino group,
Disubstitution is preferred over monosubstitution. As the substituent, an alkyl group is preferable.

The aryl group is preferably one having 6 to 36 carbon atoms, and more preferably a single ring. Specific examples include phenyl, 4-t-butylphenyl, 2-methylphenyl, 2,4,6-trimethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl, 4-dichlorophenyl and the like. General formula (II) used in the present invention
The cyan coupler represented by has an oil-solubilizing group in the molecule, is easily soluble in a high boiling organic solvent, and is formed by oxidative coupling of the coupler itself and the coupler with a color-forming reducing agent (developer). Preferably, the dye is non-diffusible in the hydrophilic colloid layer. In the coupler represented by the general formula (II), R ³ contains a coupler residue represented by the general formula (II) to form a dimer or higher multimer, or R ³ represents a polymer chain. They may be contained to form a homopolymer or a copolymer. A typical example of the homopolymer or copolymer containing a polymer chain is a homopolymer or copolymer of an addition polymer ethylenically unsaturated compound having a coupler residue represented by the general formula (II). In this case, the polymer may contain one or more types of cyan coloring repeating units having a coupler residue represented by the general formula (II). It may be a copolymer containing one or more non-color-forming ethylenic monomers which do not couple with the oxidation product of an aromatic primary amine developer such as phenol. Specific examples of the cyan coupler defined in the present invention are shown below, but the invention is not limited thereto.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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The compound represented by formula (I) can be prepared by a known method, for example, as described in JP-A-5-150423 and 5-2.
No. 55333, No. 5-202004, No. 7-4837
No. 6, 9-189988 can be synthesized.

For example, the synthesis of the exemplary compound (1) is carried out by the following route. Details of the reaction conditions and the like are described in
189988.

[0059]

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Next, the compound represented by formula (III) of the present invention will be described in detail. In the compound represented by the general formula (III), when R ^a1 or R ^a2 is an alkyl group, the sum of the carbon numbers including the substituents is 1 to 30 respectively.
Is preferable, and more preferably, it is in the range of 1 to 20. When R ^a1 or R ^a2 is an aryl group, the total number of carbon atoms including the substituent is preferably 6 to 30. When R ^a3 or R ^a4 is an alkyl group, the sum of the number of carbon atoms including the substituent is preferably in the range of 1 to 24, more preferably 1 to 18. Also ^{Ra3
Alternatively,} when R ^a4 is an aryl group, the sum of the number of carbon atoms including the substituent is preferably in the range of 6 to 24.

The group which can be substituted with an alkyl group for R ^{a1 to} R ^a4 is not particularly limited, but includes a halogen atom, an alkoxy group,
Aryl group, aryloxy group, acyl group, acyloxy group, alkoxycarbonyl group, sulfonyl group, phosphoryl group, alkylthio group, arylthio group, acylamino group, carbamoyl group, sulfamoyl group, sulfonamide group, carbamoylamino group, alkoxycarbonylamino group Are particularly preferable, and a halogen atom, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, an aryloxy group, and an acylamino group are more preferable. The group which can be substituted for the alkyl group may contain an unsaturated bond.

When R ^{a1 to} R ^a4 are an aryl group, the substitutable groups may be the same as the above-mentioned examples of the substituent of the alkyl group. Group, acyloxy group and acylamino group.

[0063] Preferred ranges number of carbon atoms of R ^a5 in the range of 6 to 0 and more preferably in the range of 6 to 24. R ^a5
Substituent groups are the same as the substituent groups on the aryl groups R ^a1 to R ^a4, it is also preferred group the same as the. The compound of the general formula (III) is used by being fixed in an oil droplet and dispersed in a hydrophilic colloid. Therefore, it is necessary to make the compound lipophilic. It is preferable that at least any one lipophilic groups R ^a1 to R ^a5 (oil-solubilizing group) is introduced, the total number of carbon atoms of R ^a1 to R ^a5 are required to be at least 14 or more is there. The total number of carbon atoms is preferably in the range of 16 to 40, and more preferably in the range of 18 to 36.

Preferred groups for introducing the oil-solubilizing group are R ^{a1 and} R ^a5 . If oil-solubilizing group is introduced into R ^a1, as the oil-solubilizing group substituted with an unsubstituted linear or branched alkyl group or an alkoxy group, an aryloxy group, an acyl group or an alkoxycarbonyl group having 12 to 24 carbon atoms The alkyl group having 12 to 36 carbon atoms is preferable, and the alkyl group having 14 to 20 carbon atoms is particularly preferable. At this time, ^Ra5 may or may not have a substituent, but is preferably unsubstituted. When an oil-solubilizing group is introduced into ^Ra5 , the oil-solubilizing group is preferably an alkyl group having 12 to 30 carbon atoms, an alkoxy group, an acyloxy group, or an acylamino group, and particularly preferably an alkoxy group having 12 to 24 carbon atoms. R ^a3 and R ^a4 are preferably hydrogen atoms. Among the compounds of the general formula (III), a compound represented by the following general formula (IV) or (V) is preferable from the viewpoint of storage stability.

[0065]

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[0066]

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Next, the compound represented by formula (IV) will be described in detail. R ^a and R ^b each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group having a total of 1 to 30 carbon atoms including the carbon number of the substituent. When R ^a and R ^b are an aryl group, the substituent that substitutes the aryl group is the substituent described in the description of R ^a1 in the formula (III), and specific examples thereof include those described in the description of R ^a1. Can be Among them, more preferred are an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an aminocarbonylamino group, and an alkoxycarbonylamino group. Most preferably, they are an alkyl group (1-10 carbon atoms), a halogen atom (chlorine atom, bromine atom), and an alkoxy group (1-10 carbon atoms). When R ^a and R ^b are aryl groups, unsubstituted aryl groups are more preferable than those having a substituent. When R ^a and R ^b are alkyl groups, the total number of carbon atoms including the number of carbon atoms of the substituent is 1 to 30. The unsubstituted alkyl group may be linear or branched. As a straight-chain alkyl, it has 1 to 1 carbon atoms.
26 (e.g., methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-octadecyl, n-eicosyl) are preferred, and the branched alkyl has 3 to 26 carbon atoms. (Eg, i-propyl, t-butyl, 2-ethylhexyl) are preferred. R
^{When a} and R ^b are substituted alkyl, the substituent is represented by the formula (II)
It is a substituent described in the description of R ^a1 in I), and the total number of carbon atoms including the number of carbon atoms of the substituent is preferably from 1 to 20. Specific examples thereof include those described in the description of ^Ra1 , and specific examples thereof include ethoxymethyl, acetoxymethyl, stearoyloxymethyl, p-phenoxymethyl, 1-nitrophenoxymethyl, 1-chlorooctyl, and the like. Is mentioned.

R ^a3 and R ^a4 represent a hydrogen atom, or a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. When R ^a3 and R ^a4 are a substituted alkyl group or a substituted aryl group, the substituent is R ^{a1 of the} formula (III)
And specific examples thereof include those described in the description of ^Ra1 . When R ^a3 or R ^a4 is an alkyl group, it preferably has 1 to 20 carbon atoms. An unsubstituted alkyl group is preferable to an alkyl group having a substituent. When R ^a3 or R ^a4 is an aryl group, it preferably has 6 to 20 carbon atoms. Preferably, at least one of R ^{a3 and} R ^a4 is a hydrogen atom, and most preferably, both R ^a3 and R ^a4 are hydrogen atoms.

R ^a5 is a substituted or unsubstituted aryl group, and the substituent substituted on the aryl group is the substituent described for R ^a1 in the formula (III). Specific examples of the substituent are also represented by the formula (I
The ones mentioned in the explanation of II) can be cited. The substituent is preferably an alkyl group (C1-20, for example, methyl, ethyl, i-propyl, t-butyl, n-octyl), an alkoxy group (C1-20, for example, methoxy, ethoxy, i-propoxy). , T-butoxy, n-octyloxy, n-tetradecyloxy, n-hexadecyloxy, n-octadecyloxy), acylamino group (1 to 20 carbon atoms, for example, acetylamino group, propionylamino, stearoylamino), alkoxy Carbonylamino (C2-20, for example, methoxycarbonylamino, ethoxycarbonylamino, octyloxycarbonylamino), aminocarbonylamino (C1-20, for example, dimethylaminocarbonylamino,
Dioctylaminocarbonylamino), alkylsulfonylamino group (1 to 20 carbon atoms, for example, methanesulfonylamino, ethanesulfonylamino, butanesulfonylamino, octanesulfonylamino), arylsulfonylamino (6 to 20 carbon atoms, for example, benzenesulfonylamino, Toluenesulfonylamino, dodecylbenzenesulfonylamino).

The compound of the formula (IV) has a structure represented by R
It is preferred that at least one of ^a , R ^b , R ^a3 , R ^a4 , and R ^a5 has a so-called ballast group. Molecular weight 2
00 or more, more preferably 250 or more, and 30 or more.
0 or more is more preferable, and 350 or more is most preferable. The compound of the formula (V) will be described in detail. R of the formula (V)
^a3 , R ^a4 and R ^a5 have the same ^{meanings as} in formula (IV). The same applies to specific examples and preferable examples. R ^c represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. When R ^c is an alkyl group or an aryl group, the substituent is the substituent described in the description of R ^{a1 in} formula (III). Specific examples thereof include those described in the description of ^Ra1 . R ^c is preferably an alkyl group (1 to 20 carbon atoms, for example, methyl, ethyl, i-propyl, t-butyl, n-octyl, n-dodecyl, n-hexadecyl, n-octadecyl, i-octadecyl,
-Ethylhexyl, 2-methoxyethyl, 2-chloroethyl) and aryl groups (C6-20, for example, phenyl, naphthyl, p-chlorophenyl, m-methoxyphenyl, o-methylphenyl).

The compound of the formula (V) has a structure represented by R
It is preferable that at least one of ^c , R ^a3 , R ^a4 , and R ^a5 has a so-called ballast group. The molecular weight is preferably 200 or more, more preferably 250 or more, still more preferably 300 or more, and most preferably 350 or more. Among the phenidone compounds represented by formulas (IV) and (V) of the present invention, when added to the non-photosensitive layer, more preferred are compounds represented by formula (IV). When added to the photosensitive layer, the compound represented by the general formula (V) is more preferable. Among the compounds represented by the general formula (V), R
Preferably, ^c is an alkyl group, R ^a3 and R ^a4 are both hydrogen atoms, and R ^a5 is a substituted or unsubstituted aryl group. Among them, those in which the aryl group of R ^a5 is unsubstituted or those in which the substituent is an alkoxy group, an acylamino group, an alkylsulfonylamino group, or an arylsulfonylamino group are preferable. More preferred. As R ^c , an unsubstituted alkyl group is more preferable than an alkyl group having a substituent. Most preferred of the compounds represented by formula (V) are those wherein R ^c is an unsubstituted alkyl group, R ^a3 and R ^a4 are hydrogen atoms, and R ^a5 is an unsubstituted aryl group. Specific examples of the compound represented by formula (IV) or (V) of the present invention are shown below, but it should not be construed that the invention is limited thereto.

[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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A method for synthesizing the compounds represented by formulas (IV) and (V) will be described. The compound represented by the general formula (IV) of the present invention can be synthesized according to the following synthesis method.

[0080]

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Compound (V) -A is condensed with hydrazine
To synthesize a compound represented by the general formula (V). Compound
(V) -A, R^dIs an alkyl group or an aryl group
R^c , R^a3 , R^a4 Is R of the general formula (V)^c, R^a3 ,
R^a4 Is synonymous with Hydrazine R^a5 Is the general formula (V)
R^a5 Is synonymous with This reaction is performed in an appropriate solvent
It is preferable to make the above base act. Hydrazine
When using a salt, add 2 equivalents to release hydrazine.
It is preferred to use at least the amount of base. As the base,
Alkoxides are preferred, potassium-t-butoxide,
Sodium methoxide and the like are mentioned as examples.
Solvents include n-butanol, t-butanol,
Examples include tyl sulfoxide and dimethylacetamide.
It is mentioned. The reaction temperature is generally between -20 ° C and 180 ° C.
Although it can be performed, it is preferably 0 ° C to 120 ° C, more preferably
Or 30 ° C to 90 ° C. Reaction time is generally 5 minutes
24 hours is appropriate, but preferably 30 minutes to 6:00
And more preferably from 1 hour to 3 hours. Hi
The use ratio of drazine and compound (V) -A is a molar ratio.
2: 1 to 1: 2 are preferred. More preferably, 1.2:
1-1: 1.2.

The compound represented by the general formula (IV) is synthesized by reacting the general formula (IV) -A with hydrazine. In the general formula (IV) -A, R ^a , R ^b , R ^a3 and R ^a4 are represented by the general formula (I
It has the same meaning as ^Ra , ^Rb , ^Ra3 and ^{Ra4 in} V). L ¹ ,
L ² is a group that leaves in a nucleophilic reaction. L ¹ is preferably a halogen atom or an oxygen atom activated by a condensing agent. L ² is preferably a hydroxy group,
It is a halogen atom. The reaction temperature is generally -20 ° C to 18
Although it can be performed at 0 ° C., it is preferably 0 ° C. to 120 ° C., and more preferably 30 ° C. to 90 ° C. The reaction time is generally from 5 minutes to 24 hours, but is preferably from 1 hour to 6 hours. In the reaction of compounds (IV) -B to (IV), acidic conditions are preferred when L ² is a hydroxyl group. When L ² is a halogen atom, the reaction may be performed under any of neutral, acidic and alkaline conditions.

Synthesis of Compound (52) Exemplary Compound 52 was synthesized by the following route.

[0084]

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(1) First Step 256 g (1.94 mol) of methyl succinate and 800 ml of methanol were stirred at room temperature, and 375 g (1.94 mol) of sodium methylate (28% by weight) was added dropwise thereto. Then, 592 g of 1-bromohexadecane
(1.94 mol) was added dropwise. After refluxing for 3 hours, methanol was distilled off, and the reaction solution was poured into 1N aqueous hydrochloric acid. After extraction with hexane, washing with brine and drying, the solvent was distilled off to obtain 511 g (1.43 mol) of an intermediate A (yield: 73.7).
%).

(2) Second step: 511 g (1.43 mol) of intermediate A and methanol 8
A solution prepared by dissolving 94.6 g (1.43 mol) of potassium hydroxide (85%) in 800 ml of methanol was added dropwise to 00 ml of the solution while stirring at 35 ° C. After reacting at 40 ° C. for 2 hours, a solution obtained by dissolving 130 ml of concentrated hydrochloric acid in 500 ml of water was further added dropwise. The precipitated crystals are collected by filtration, and water and n
-Washing with hexane gave Intermediate B. Intermediate B was used in the next step without drying.

(3) Third Step Intermediate B (total amount: 1.43 mol) and methanol 1.0
Liters, and stirring at 20 ° C. with diethylamine 1
15 g (1.57 mol) were added dropwise. Then 3 more
135 g (1.57 mol) of a 5% aqueous folimarin solution was added dropwise and reacted at 20 ° C. for 24 hours. The precipitated crystals were collected by filtration, washed with water and methanol, and then dried to obtain 396 g (1.28 mol) of intermediate C (yield: 89.5).
%).

(4) Fourth Step 145 g (1.34 mol) of phenylhydrazine and 1.5 l of toluene were stirred at 140 ° C., and the solvent was distilled off using a Dean-Stark dehydrator until the internal temperature reached 100 ° C. . Subsequently, sodium methylate (28% by weight)
After dropping 272 g (1.41 mol) of methanol and distilling off methanol, a solution of 396 g (1.28 mol) of the intermediate C in 400 ml of toluene was dropped. After refluxing for 30 minutes,
After cooling on ice, 150 ml of concentrated hydrochloric acid was added.
0 ml was added. The insoluble matter was removed by filtration, and the solution was cooled. After the precipitated crystals were collected by filtration, washed with water and n-hexane, and dried, 393 g of compound (51) (1.02
mol) was obtained (yield 79.7%). Other compounds can be synthesized similarly.

The effect of using the compound represented by the general formula (III) of the present invention is as follows: when a highly active cyan coupler having a pKa of 8.7 or less is used,
It is intended to improve problems such as cyan stain and color mixing during processing without significantly affecting other photographic performances, and is an effect commonly seen in combination with a cyan coupler having a pKa of 8.7 or less. The cyan coupler of the present invention has a feature that the pKa is low due to its structure.
The use of the compounds of I) is particularly effective. The effect is particularly large when the pKa of the cyan coupler of the present invention is 8.0 or less, and even more advantageous when the pKa is 7.5 or less, which is particularly preferable. The pKa of the coupler is TH
According to a pH titration curve in an F / water = 6/4 mixed solvent system,
It can be easily measured by determining the pH at the point where it has been neutralized by exactly half. The compound represented by formula (III) of the present invention can be used together with a cyan coupler in a cyan coloring layer. In this case, the general formula (V)
It is more preferable to have a structure represented by the following formula, since the effect is greater and the influence of a decrease in color development is small.
The compound of the general formula (III) can be used for a non-photosensitive colloid layer. In this case, it is desirable to use in combination with a known color mixing inhibitor such as hydroquinones. When used in the non-photosensitive layer, the compound of the general formula (III) is more preferably a compound of the structure represented by the general formula (IV) from the viewpoint of its effect.

The preferred coating amount of the cyan coupler of the present invention depends on the molar extinction coefficient of the cyan coupler.
In the range of 01~1g / m ^2, preferably 0.05 to 0.
5 g / m ² . When the cyan coupler to be used is a coupler represented by the general formula (II), the preferred amount is in the range of 0.01 to 0.6 g / m ² , more preferably 0.05 to 0.4 g / m ^2. m ² , more preferably 0.1
０．３0.3 g / m ² . The ratio of the amount of the cyan coupler to the amount of the silver halide used depends on the equivalentity of the coupler, and the 2-equivalent coupler has an Ag / coupler ratio of 1.5 to 8,4.
For equivalent couplers, the range is 3-16. In the present invention, 2-equivalent couplers having a low pKa are preferred, in which case the Ag / coupler ratio is in the range 1.5-8, preferably 2-5.
6, more preferably in the range of 2.5-5.

In the present invention, general formulas (III) and (I
The compound represented by (V) or (V) is a surfactant or the like in a non-photosensitive hydrophilic colloid layer together with an organic compound such as a high-boiling organic solvent, a color mixing inhibitor, an ultraviolet absorber, or a polymer dispersant. Can be used together with a dispersing agent. The amount used is in the range of 0.1 mol% to 200 mol%, preferably 1 to 100 mol%, more preferably 5 to 50 mol%, based on the cyan coupler to be coated. It is preferred that the compound represented by formula (III), (IV) or (V) of the present invention is used simultaneously with the non-photosensitive colloid layer as well as the cyan coloring layer. In this case, the amount used in the cyan coloring layer is 1 to the cyan coupler.
It is in the range of -100 mol%, preferably in the range of 5-50 mol%. The compound of the general formula (III), (IV) or (V) can also be preferably used in combination with the layers other than those described above. In this case, the total amount used is in the range of 1 to 200 mol% based on the cyan coupler. , More preferably 5 to 10
0 mol%, more preferably in the range of 10 to 50 mol%.

The cyan couplers of the present invention may further include, in addition to the above compounds, compounds represented by the following formulas (VI), (VII), (VIII) and (IX) in terms of adjusting hue and promoting color formation. It is preferred to use one of the following. These compounds can be used in combination of several types depending on the purpose. General formula (VI)

[0093]

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In the general formula (VI), the substituent R ^s is an alkyl group,
Represents an alkoxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group or a sulfonyl group. These substituents may further have a substituent such as a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, and an ester group. The substituent R ^s is preferably an alkoxy group or an alkoxycarbonyl group, and most preferably an alkoxy group. The substitution position of the substituent R ^s may be ortho, meta or para to the COOH group, but is preferably ortho to the hue adjusting ability. The benzene ring may further have a substituent such as a halogen atom or an alkyl group. General formula (VII)

[0095]

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In the general formula (VII), the substituent R ^t is an alkyl group,
Represents an alkoxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group or a sulfonyl group. These substituents may further have a substituent such as a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, and an ester group. The substituent R ^t is preferably an alkoxy group or an alkoxycarbonyl group, and most preferably an alkoxy group. Ortho substitution position CONH2 group substituents R ^t, meta, para -
Either one may be used, but the ortho position is preferred from the viewpoint of hue adjusting ability. Further halogen atoms on the benzene ring,
It may have a substituent such as an alkyl group. General formula (VIII)

[0097]

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In the general formula (VIII), the substituents R ^u , R ^v , R ^w and R ^x may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group or an acyl group. These substituents may further have a substituent such as a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, and an ester group. Substituents R ^u, R ^v, R ^w and a are preferably R ^x hydrogen atom, an alkyl group or an aryl group, an alkyl group or a cycloalkyl group is more preferably a cycloalkyl group branch is most preferred. The substitution position of the two carbamoyl groups may be ortho, meta or para-,
It is particularly preferred to be in the meta position in terms of hue adjusting ability. The benzene ring may further have a substituent such as a halogen atom or an alkyl group. General formula (IX)

[0099]

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In the general formula (IX), the substituent Q represents a> N—R ^y group or a> C (R ^y1 ) R ^y2 group. The substituents R ^y , R ^y1 and R ^y2 each represent a hydrogen atom, an alkyl group, an aryl group,
Represents an alkoxycarbonyl group or an acyl group. Also,
The substituent R ^z represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group or an acyloxy group. These substituents may further have a substituent such as a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, and an ester group. The substituent R ^y is preferably an alkyl group or an aryl group, and more preferably an alkyl group substituted with a linear or branched alkyl group or an aryl group. The substituent R ^z is preferably an alkyl group or an alkoxy group, more preferably an alkoxy group.
R ^y1 and R ^y2 are preferably a hydrogen atom or an alkyl group.

The following formulas (VI), (VII) and (VII)
Specific examples of the compounds represented by I) and (IX) will be given, but the compounds preferably used in the coupler of the present invention are not limited to the following.

[0102]

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[0103]

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[0104]

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[0105]

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In order to introduce the cyan coupler and the like into the silver halide photosensitive material, known dispersion methods such as an oil-in-water dispersion method and a latex dispersion method using a high-boiling organic solvent described later can be used. In the oil-in-water dispersion method, a cyan coupler or other photographically useful compound is dissolved in a high-boiling organic solvent, and the dispersion is dispersed in a hydrophilic colloid, preferably in an aqueous gelatin solution, together with a dispersing agent such as a surfactant, using an ultrasonic, colloid mill. It can be emulsified and dispersed into fine particles by a known device such as a homogenizer, a Menton-Gaulin, a high-speed dissolver, or the like. In dissolving the coupler, an auxiliary solvent can be further used. The auxiliary solvent referred to here is an organic solvent effective at the time of emulsification and dispersion, and refers to one that is substantially removed from the photosensitive material after the drying step at the time of coating, for example, ethyl acetate, acetate of a lower alcohol such as butyl acetate, Examples include ethyl propionate, secondary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, methyl carbitol acetate, methyl carbitol propionate, and cyclohexanone.

Further, if necessary, an organic solvent which is completely miscible with water, for example, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, dimethylformamide and the like can be partially used in combination. These organic solvents can be used in combination of two or more kinds. Further, from the viewpoint of improving the aging stability during storage in the emulsified dispersion state, suppressing photographic performance changes and improving the aging stability of the final composition for coating mixed with the emulsion, the emulsified dispersion may be depressurized as necessary. All or a part of the auxiliary solvent can be removed by a method such as distillation, noodle washing or ultrafiltration. The average particle size of the lipophilic fine particle dispersion thus obtained is preferably from 0.04 to 0.50 μm, more preferably from 0.05 to 0.30 μm, and most preferably from 0.08 to 0.20 μm. It is. The average particle size was measured using the Coulter Submicron Particle Analyzer mode.
1 It can be measured using N4 (Coulter Electronics Co., Ltd.) or the like.

In the oil-in-water dispersion method using a high-boiling organic solvent, the weight ratio of the high-boiling organic solvent to the total weight of the cyan coupler used can be arbitrarily determined, but is preferably 0.1%.
Or more, and 10.0 or less, more preferably 0.3 or more and 7.0 or less, and most preferably 0.5 or more and 5.0 or less. It is also possible to use a high boiling point organic solvent without using it at all.

For the cyan coupler of the present invention, 2-acylamino-5-alkylphenol type cyan coupler, 2,5-diacylaminophenol type cyan coupler and 2-carbamoyl-1-type
A naphthol type cyan coupler can be used in combination.
Among them, a combination with a 2-acylamino-5-alkylphenol-type cyan coupler is particularly preferable. In this case, the cyan coupler to be used in combination is 1 to the coupler of the present invention.
It is in the range of 50 mol%, preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

In order to improve the image fastness of the cyan coupler of the present invention, a method of co-dispersing an organic solvent-soluble water-insoluble polymer in oil droplets is also preferably used. In this case, the polymer is preferably a styrene, acrylamide, methacrylamide, acrylate, methacrylate-based polymer or a copolymer thereof, and the number average molecular weight is preferably in the range of 20,000 to 200,000. In order to improve the stability of the emulsion, an oligomer molecule having a molecular weight of about 500 to 5,000 is preferably used, and a styrene oligomer, an α-methylstyrene oligomer and the like are preferable. In particular, styrene and α-
Methylstyrene oligomers are particularly preferred in terms of solubility. It is also preferable to add an amphiphilic polymer to the coating solution to promote color formation. In this case, a copolymer of acrylic acid or methacrylic acid and these esters is more preferred. Particularly, a copolymer of methacrylic acid and butyl acrylate is a particularly preferable compound having a large effect.

The silver halide photographic light-sensitive material to which the present invention is applied may be any of a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc., and among them, a color photographic paper is preferable.
As the photographic support used in the present invention, a transmission type support or a reflection type support can be used. As the transmission type support, a transmission film such as a cellulose triacetate film or polyethylene terephthalate,
A material in which an information recording layer such as a magnetic layer is provided on a polyester of 6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) or a polyester of NDCA, terephthalic acid and EG is preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable.

Further, it is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
Pyrazoline-based fluorescent whitening agents can be used, and more preferred are benzoxazolylnaphthalene-based and benzoxazolylstilbene-based fluorescent whitening agents. Specific examples of the fluorescent whitening agent contained in the water-resistant resin layer include, for example, 4,4 ′
-Bis (benzoxazolyl) stilbene or 4,4'-
Bis (5-methylbenzoxazolyl) stilbene and a mixture thereof are exemplified. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by weight, more preferably 0.001 to 0.5% by weight, based on the resin. The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

As the silver halide emulsion used in the present invention, silver chloro (iodide), silver chloro (iodo) bromide, silver (iodo) bromide emulsion and the like are used. A silver chloride or silver chlorobromide emulsion having a silver content of 95 mol% or more is preferable, and a silver halide emulsion having a silver chloride content of 98 mol% or more is preferable. Among such silver halide emulsions, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable since high sensitivity can be obtained and photographic performance can be stabilized.

The above-mentioned reflective support comprises a silver halide emulsion,
Further, different metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), Cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (anti-stain and anti-fading agents), dyes (colored layers), gelatin species, layer composition of photosensitive material, coating pH of photosensitive material, etc. As described above, those described in the patents of Tables 1 and 2 can be preferably applied to the present invention.

[0115]

[Table 1]

[0116]

[Table 2]

The cyan, magenta and yellow couplers used in the present invention include those described in
No. 2-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6, JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column, last line and page 30, upper right Lines 6 to 35, lower right column, line 11 and EP 0355, 660A2, page 4, lines 15 to 27, page 5, line 30 to page 28, last line, page 45, lines 29 to 31 Eyes, page 47, lines 23-6
The couplers described on page 3, line 50 are also useful.

As the antibacterial and antifungal agents that can be used in the present invention, those described in JP-A-63-271247 are useful.
Gelatin is preferred as the hydrophilic colloid used in the photographic layer constituting the light-sensitive material. Particularly, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably at most 5 ppm, more preferably at most 3 ppm. .

The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. Various light emitters that emit light in a spectral region are used as necessary for a cathode ray tube used for image exposure. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode ray tube also has a phosphor which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, the cathode ray tube is exposed. The image signal of a plurality of colors may be input to the display unit to emit light from the display screen. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
In general, plane-sequential exposure is preferable for high image quality because a cathode ray tube with high resolution can be used.

The photosensitive material of the present invention is a second harmonic generation light source (SHG) in which a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a solid laser using a semiconductor laser as an excitation light source is combined with a nonlinear optical crystal.
And the like, and is preferably used for a digital scanning exposure method using monochromatic high density light. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) in which a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used.
In a solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength ranges of blue, green and red. The exposure time in such a scanning exposure is defined as the time for exposing a pixel size in the case of a 400dpi pixel density, the preferred exposure time 10 ^{- 4} seconds or less, more preferably 10 ^-6 sec or less.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table.

The cyan coupler represented by the general formula (I) according to the present invention and the 3-pyrazolidone derivative represented by the general formula (III) preferably used in combination are described above, and these compounds are used. The explanation of the silver halide photographic light-sensitive material is finished, and then the drying step and the drying method in the developing step according to the present invention will be described.

First, the drying method of the present invention will be described with reference to the accompanying drawings of one embodiment. However, the present invention is not limited to only this embodiment. FIG. 1 shows a silver halide photographic color paper processing machine to which the present invention is applied. The present processing machine develops, bleach-fixes, rinses with water, and then dries a web-shaped color paper exposed based on a positive document to form an image on the color paper. Although the effect of the present invention is not limited to color paper, color paper is an embodiment in which the effect of the invention is particularly large. The color paper processed by the processing machine is preferably 98.
A silver halide color photographic light-sensitive material 11 having at least one layer of a silver halide emulsion containing at least one mol% of silver chloride on a support, which is colored by a color developing solution containing an aromatic primary amine color developing agent. Developed.

In FIG. 1 showing the main body of the developing machine, the main body 10 of the developing machine includes a developing tank 2, a bleach-fixing tank 4, and a washing tank 6a to 6c.
6e, a drying unit 7 is provided, and the photosensitive material 11 after exposure is
After being developed, bleach-fixed, washed with water and dried, it is taken out of the processing machine body 10. The photosensitive material 11 is a pair of conveying rollers 4 and 14.
By immersion in a processing solution for a predetermined time while being nipped and conveyed with the emulsion side down, color development processing is performed, then bleach-fixing is performed to remove developed silver and residual silver halide, and a dye image is formed on the support. Is done. The photosensitive material is then conveyed to a washing tank 6. The space between the washing tanks 6a to 6e is transferred in the liquid via a blade 94 provided on the wall of the tank. Although various plastic materials can be used for the submerged blade 94, polyurethane rubber is particularly preferable from the viewpoint of elasticity and durability for liquid sealing. In each tank, blocks 29 are arranged at various places to prevent the photosensitive material 11 from being clogged. Wash tanks 6a to 6e are 5
The tanks are arranged, and each tank is cascaded. The cleanliness of the washing water is gradually reduced from the last tank 6e to the first tank 6a. The washing tank is provided with a reverse osmosis membrane (RO membrane) device 90, and water in the fourth washing tank 6d is pumped to the reverse osmosis membrane device 90 by the pump 30, and the reverse osmosis membrane device 90 is provided.
Is supplied to the fifth washing tank 6e,
The concentrated water that has not passed through the reverse osmosis membrane device 90 is supplied to the fourth washing tank 6d.

A circulating liquid spray nozzle (2 mm in diameter) for stirring by a pump 92 is provided on the wall of each tank and on the block 29.
In particular, the developing tank 2 has a variable flow rate in the range of 0.5 to 12 liters / minute by adjusting a pump or the like, and a liquid to be jetted onto the surface of the photosensitive material in accordance with the blowing amount. , That is, the intensity of stirring can be adjusted.

The photosensitive material 11 having been subjected to the water-washing process passes through the heat rollers 14A and 16A and is conveyed to the drying section 7 by the conveying roller pairs 14 and 16. The drying unit 7 is an automatic developing machine 10
The photosensitive material 11 is provided in a box-shaped casing of
And a hot air generator 22 as shown in FIG.

[0129] As shown in FIG.
Has a belt 28 and a tension roller 91 for applying tension to the belt 28, and the belt 28 is driven in a counterclockwise direction in FIG. 1 by a motor (not shown). In this belt conveyor 20, the rollers 3
Straight portion 28A of belt 28 located above 0, 31
Is a transport portion for transporting the photographic paper 11, and the photographic paper 11 is transported horizontally in the direction of the arrow L by the linear portion 28A.

A chamber 32 is provided above the belt conveyor 20 at a predetermined interval. The chamber 32 has a rectangular box shape that is long along the conveying direction of the belt conveyor 20, and a lower plate member 34 is provided in parallel with the linear portion 28 </ b> A of the belt 28.

As shown in FIG. 3, a plurality of long holes 36 are formed in the width direction of the plate 34 in the vicinity of the upstream end of the photographic paper 11 in the transport direction (the direction opposite to the arrow L direction). They are formed at predetermined intervals along (in the direction of arrow W).

As shown in FIG. 1 and FIG.
On the lower side, a shaft 38 rotatably supported by the side wall 32A of the chamber 32 is arranged along the width direction of the plate member 34. The shaft 38 has a long hole 36
The roller 40, a part of which protrudes from the upper surface of the plate member 34,
It is installed corresponding to.

A plurality of long holes 42 are formed at predetermined intervals along the width direction (arrow W direction) of the plate member 34 near the end of the plate member 34 on the downstream side in the transport direction of the photographic paper 11. A shaft 44 and a shaft 46 rotatably supported by the side wall 32 </ b> A of the chamber 32 are arranged below the long holes 42 in parallel along the arrangement direction of the long holes 42. These shafts 44 and 46 are provided with the plate material 34 through the long holes 42.
A roller 40 having a part protruding from the upper surface thereof is mounted corresponding to the elongated hole 42.

As shown in FIG. 2 (the vertical relationship is reversed with respect to the installed state of the drying unit in FIG. 1), a hot air generator 22 is provided on the side of the chamber 32. The hot air generator 22 includes a casing 50 integrally connected to the chamber 32, and a fan 52 and a heater 54 are provided in the casing 50. The fan 52 heats the air sucked from the hole 56 formed in the upper part of the casing 50 by the heater 54, and the hole 5 formed in the side wall 22A.
The air is blown into the chamber 32 through. Heater 54
Has a dense heating wire density in the first half of the air drying section,
The output is higher than that in the latter half of the blow drying unit.

As shown in FIG. 3, the plate 34 of the chamber 32 has a plurality of holes 58 formed in the direction in which the photographic paper 11 is transported. The portion of the plate 34 where the holes 58 are formed corresponds to the perforated plate of the present invention. Hole 58 of the present embodiment
Is a circular hole having an inner diameter D, which is arranged so that the direction perpendicular to the transport direction of the photographic paper 11 is a pitch P ₁ , the transport direction of the photographic paper 11 is a pitch P ₂ , and a staggered shape as a whole. ing.

Here, when the warm air is blown into the chamber 32, the warm air is blown out from the hole 58 at right angles to the linear portion 28A of the belt 28 as shown by the arrow A in FIG. As shown in FIG. 2, the hot air blown out from the hole 58
Is sucked from. The hot air generator 22 sucks a part AH of the hot air blown out from the hole 58 and also sucks outside air outside the apparatus from a slit-shaped outside air introduction hole 62 provided in the casing 18 of the automatic developing machine 10. It is supposed to.

As shown in FIG. 1, on the discharge side of the printing paper 11 of the belt conveyor 20, the dried printing paper 11 is carried out to a sorter (in the direction of arrow B) or a densitometer (in the direction of arrow C) which is not shown. A transfer device 64 is provided. As shown in FIGS. 1 and 2, inside the chamber 32, a hot air temperature control sensor that detects the temperature of the hot air in the chamber 32 at a position shifted to the upstream side from the center in the transport direction of the photographic paper 11. 66 are provided. The hot air temperature control sensor (for example, a thermistor, a thermocouple, etc.) 66 is connected to a control device (not shown), and the control device controls the output of the heater 54 so as to maintain the temperature of the hot air at the treatment temperature.

Next, the process of processing the photosensitive material in the processing apparatus of this embodiment will be described. The photographic paper 11 which has been subjected to the rinsing process is passed through a developing tank, a bleach-fixing tank, a rinsing tank, and the like (not shown).
The excess water adhering to the surface is removed by a nip roller (not shown), and then transported to the drying unit 7 by the transport roller pairs 14 and 16. The heating of the photographic paper 11 by the heat roller is performed by using the transport roller 14A and the transport roller 16A.
A (see FIG. 1) is a heat roller. In this case, it is preferable to set the temperature of the upstream transport roller 14A in the transport direction higher than the temperature of the downstream transport roller 16A.

When the printing paper 11 is heated by the heater, the printing paper 11 may be heated by irradiating the heat (infrared ray) generated by the halogen lamp heater to the printing paper 11 in addition to the contact heating by the heat roller as described above. . Subsequent to contact heating, blast drying is performed. The photographic paper 11 that has reached the drying unit 7 is
The belt 28 is conveyed in the direction of arrow L while being pressed against the linear portion 28A of the belt 28 by the warm air blown out from the holes 58 toward the belt 28 (see FIG. 1).

The photographic paper 11 conveyed while being pressed against the belt 28 first has heat rollers 14A and 16A.
, And the moisture adhering to the surface is evaporated.
In the first half of the drying unit 7, most of the heat supplied to the printing paper 11 by heat is taken away as latent heat of evaporation, and the printing paper 1
1 is kept constant at a temperature lower than the temperature of the heat roller. Thereafter, the photographic paper 11 is transported to the latter half area where the holes 58 are formed. At this stage, since the amount of heat supplied by the warm air is greater than the latent heat taken by the evaporated water, the surface temperature of the photographic paper 11 increases (drying at a reduced rate).

The photographic paper 11 dried in the drying unit 7 is thereafter transferred to a sorter (not shown)
Direction) or the densitometer (direction of arrow C).

In the present embodiment, the printing paper 11 is dried by the heat from the heat rollers 14A and 16A in the first half of the drying, so that the hot air blown out of the slit in the direction orthogonal to the transport direction. Constant-rate drying can be performed with a shorter transport distance (short time) than in the case of drying. In the latter half of the drying section 7, warm air is uniformly blown in the direction orthogonal to the transport direction of the photographic paper 11 by the holes 58, and the drying is performed at a reduced rate. Will not occur. The blast drying is a rate-decreasing drying, which greatly depends on the air volume, and the influence of the temperature is small.

By the way, a part of the warm air blown on the photographic paper 11 is sucked by the fan 52 and sent again into the chamber 32. However, in the first half of the blast drying unit, a large amount of water evaporates. Since the temperature of the hot air decreases after it is used for drying, the temperature of the hot air tends to decrease. However, the temperature is hard to decrease due to a high heater output in the first half of the blow drying unit. Furthermore, by disposing the hot air temperature control sensor 66 at a position shifted toward the inlet side from the center of the air drying unit, the drying temperature can be accurately detected in the first half of the air drying unit, and the temperature of the hot air can be accurately maintained. it can. Further, the hunting width can be controlled to be small. This makes it possible to equalize the difference in dryness for each sample during the continuous processing and to shorten the required drying path length as compared with the related art. Increase in cyan dye image density over time after development processing of the cyan coupler-containing photosensitive material according to the present invention by performing dry strengthening by direct blowing of hot air after contact heating with a heat roller as described above No image stabilizes.

Therefore, in this embodiment, the printing paper 11
Can be dried efficiently and quickly with high quality. Further, in the present embodiment, since the drying efficiency can be increased by improving the shape of the outlet from which the warm air is blown, the energy consumption can be increased, and the warm air generator 2 can be increased.
2 does not lead to an increase in size, an increase in noise, an increase in cost, an increase in size, or the like.

In this embodiment, in order to increase the amount of fresh air taken in, the length of the outside air introduction hole 62 is shortened in the latter half of the blast drying, but instead of changing the opening area of the outside air introduction part between the first half and the second half. The same effect can be obtained even if the width of the hole 56 of the casing 50 in FIG. Further, as another method, the fan 52 may be provided only in the first half of the blow drying unit, or a fan having a different blowing capacity between the first half and the second half may be provided. In addition, in the plate member 34 of the embodiment, the hot air is blown out from the large number of holes 58. However, the hot air is blown into a plurality of nozzles protruding toward the photographic paper 11 as shown in FIGS. 4 and 5, for example. The warm air may be blown from the tip of the round pipe 68 as shown by the arrow A in FIG.

Further, the shape of the portion from which the warm air is blown out may be a shape other than a circle, or may be an elliptical shape or the like.
However, as shown in FIG. 6, the size of the portion where the warm air blows out is a in the direction along the transport direction (the direction of the arrow L) of the photographic paper 11 (not shown in FIG. 6). Preferably satisfies the relationship of 1 ≦ b / a ≦ 10, where b is the dimension in the orthogonal direction.

The outlet is advantageous in that the shape of the outlet is narrowed toward the inside of the chamber because the pressure loss is small and the effect of spraying the surface of the photosensitive material 11 is large. An example of a specific shape is shown in FIGS. 7 and 8 of JP-A-9-133998. Similarly, the drying air may be blown near the surface of the photosensitive material 11 through a round pipe 68 type blower. An example of such a case is also shown in FIGS.

In order to prevent drying unevenness, as shown in FIGS. 14 and 15 of JP-A-9-133998, as a specific example, it is necessary for hot air to uniformly act on the photographic paper 11. There is. Therefore, the hot air blown out from the hole 58 (or the pipe 68) of the plate member 34 may be caused to flow in the transport direction after hitting the belt 28 and the photographic paper 11, and may be reduced in the drying area (particularly in the air drying area). Hot air generator 2 in the direction orthogonal to the transport direction of the photographic paper 11
The printing paper 11 is provided with a nozzle for blowing out the hot air generated in Step 2.
Hot air may be blown in a direction perpendicular to the conveying direction of the air. In order to prevent uneven drying, the holes 58 are preferably arranged in a staggered manner.

In the combination drying of the contact heating method and the hot air blowing method according to the present invention as described above, quick drying can be performed as compared with the drying by only the hot air or only the contact heating. It is thought that rapid drying is possible to efficiently eliminate the drying resistance of the film throughout the constant rate drying period and the decreasing rate drying period, but the image stabilizing effect of the present invention is manifested by the above drying conditions. doing. The air flow is for removing the film to make it in a turbulent flow state. The larger the air amount is, the thinner the film is, the more the heat transfer effect is achieved, and effective constant-rate drying is performed.
Therefore, the effect is obtained when the mass velocity is 1000 kg / m ² · hr or more, preferably 1100 kg / m ² · hr or more, and more preferably 1200 kg / m ² · hr or more. The upper limit is 4000kg due to equipment limitations.
/ M ² · hr or less. In this case, the mass velocity is used in a commonly used meaning. That is, the density of hot air (kg / m ² ), the opening ratio of the blowing nozzle (the ratio of the unit area of the heat receiving surface and the sum of the opening areas of the nozzles or slits provided therein), the wind speed (m / sec) and the time -Expressed as the product of the second conversion coefficient (3600 sec / hr). In this case, the heat receiving area refers to an area corresponding to the photographic paper of the blow drying unit, that is, an area equal to the photographic paper. If the photographic paper is a sheet, the area corresponds to the size of the sheet. If so, it is the area of the photographic paper in the air drying section. Therefore, the sum of the opening areas of the nozzles or slits provided in the heat receiving surface refers to the sum of the opening areas of the nozzles or slits included in the portion of the blow drying unit facing the photographic paper. Further, the heat roller temperature is preferably 60 to 120 ° C, more preferably 80 to 100 ° C. In blast drying,
Since the mass speed is dominant in drying and the influence of the temperature is small, a wide range of temperature from room temperature to 150 ° C can be selected, but the preferred blowing temperature is 50 to 120 ° C, more preferably 70 to 100 ° C. It is.

The drying method of the development processing in the present invention has been described above. Next, the development processing steps and methods other than the drying will be described. In the processing method of the present invention, specifically, color development processing and desilvering processing are performed, and usually, washing and / or stabilizing processing and drying processing are performed. The color developer contains a known color developing agent. A preferred example is a p-phenylenediamine derivative, representative examples of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine d-2 4-amino-N, N-diethyl-3-methylaniline d-3 4-amino-N- (β-hydroxyethyl)-
N-methylaniline d-4 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline d-5 4-amino-N-ethyl-N- (β-hydroxyethyl) -3-methylaniline d- 6 4-amino-N-ethyl-N- (3-hydroxypropyl) -3-methylaniline d-7 4-amino-N-ethyl-N- (4-hydroxybutyl) -3-methylaniline d-8 4 -Amino-N-ethyl-N- (β-methanesulfonamidoethyl) -3-methylaniline d-9 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline d-10 4-amino -N-ethyl-N- (β-methoxyethyl) -3-methyl-aniline d-11 4-amino-N- (β-ethoxyethyl) -N
-Ethyl-3-methylaniline d-12 4-amino-N- (3-carbamoylpropyl-NN-propyl-3-methylaniline d-13 4-amino-N- (4-carbamoylbutyl-
Nn-propyl-3-methylaniline d-14 N- (4-amino-3-methylphenyl) -3
-Hydroxypyrrolidine d-15 N- (4-amino-3-methylphenyl) -3
-(Hydroxymethyl) pyrrolidine d-16 N- (4-amino-3-methylphenyl) -3
-Pyrrolidine carboxamide

Of the above-mentioned p-phenylenediamine derivatives, particularly preferred are the exemplified compounds d-5, d-6, d-7, d
-8 and d-12. Among them, d-5 and d-8 are preferable. Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, p-toluenesulfonic acid and the like may be used.
The amount of the aromatic primary amine developing agent to be used is preferably 2 mmol to 200 mmol, more preferably 12 mmol to 200 mmol, more preferably 12 mmol to 150 mmol per liter of developer. In the practice of the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, "substantially free" means that the benzyl alcohol concentration is preferably 2 ml / liter or less, more preferably 0.5 ml / liter or less, and most preferably no benzyl alcohol is contained.

More preferably, the developer used in the present invention does not substantially contain sulfite ions. Sulfite ions have a function of dissolving silver halide and reacting with an oxidized form of the developing agent, and at the same time, function as a preservative of the developing agent to reduce the dye-forming efficiency. Such an action,
It is presumed to be one of the causes of the increase in the fluctuation of the photographic characteristics due to the continuous processing. Here, the term "substantially not contained" means preferably
It has a sulfite ion concentration of 3.0 × 10 ⁻³ mol / liter or less, and most preferably contains no sulfite ion at all. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded. The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. This is because hydroxylamine itself has silver developing activity at the same time as functioning as a preservative of the developer, and fluctuations in the concentration of hydroxylamine are considered to greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the hydroxylamine concentration is preferably 5.0 × 10 ⁻³ mol / liter or less, and most preferably contains no hydroxylamine.

The developer used in the present invention more preferably contains an organic preservative in place of the above-mentioned hydroxylamine and sulfite ions. Here, the organic preservative refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a photosensitive material. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused amines, etc. It is an effective organic preservative. These are disclosed in JP-A-63-4235, JP-A-63-30845, and JP-A-63-21647.
Nos. 63-44655, 63-53551, 63-43140, 63
-56654, 63-58346, 63-43138, 63-146041
No. 63-44657, No. 63-44656, U.S. Pat.
No. 3, 2,494,903, JP-A-52-143020, JP-B-48-143
It is disclosed in each gazette or specification such as 30496.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
No. 0588, salicylic acids, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat.
An aromatic polyhydroxy compound described in the specification of JP-A No. 4 and the like may be contained as necessary. In particular, addition of alkanolamines such as triethanolamine, dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferred. Among the organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred.
JP-A 1-97953, JP 1-186939, JP 1-186940, JP 1-97953
No. 187557, and the like. It is more preferable to use the hydroxylamine derivative or the hydrazine derivative in combination with an amine in terms of improving the stability of the color developing solution, and further improving the stability during continuous processing. Examples of the amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other amines described in JP-A-1-1869.
Amines such as those described in JP-A Nos. 39 and 1-187557 are exemplified.

In the processing according to the present invention, it is preferred that the color developer contains 3.5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l of chloride ions. Particularly preferably, 4 × 10 ^-2 or more
It is 1 × 10 ^-1 mol / l. Chloride ion concentration is 1.5
When the amount is more than × 10 ^-1 mol / l, it has a disadvantage of delaying the development, and is not preferable in achieving rapid and high maximum density. On the other hand, if it is less than 3.5 × 10 ^-2 mol / l, it is not preferable in preventing fog. In the processing according to the present invention, bromine ions in the color developer
It is preferably at most 1.0 × 10 ⁻³ mol / l.
More preferably, it is at most 5 × 10 ⁻⁴ mol / l.
When the bromine ion concentration is higher than 1 × 10 ⁻³ mol / l, the development is delayed, and the maximum concentration and the sensitivity are reduced. Here, the chloride ions and bromine ions may be directly added to the developing solution, but since they are eluted from the photosensitive material to the developing solution during the developing process, the by-products of the developing process and the directly added portion may be added to the developing solution. The concentration of the replenisher or the like is adjusted so that the composition becomes appropriate. When directly added to a color developer, as a chloride ion supplying substance, sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride,
Examples thereof include magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, and among them, preferred are sodium chloride and potassium chloride. In some cases, it is supplied from a fluorescent whitening agent added to the developer. Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, preferred are potassium bromide,
Sodium bromide. When eluted from the photosensitive material during the development processing, the chloride ion and bromine ion are both supplied from the emulsion in the largest amount, but may be supplied from components other than the emulsion as described above.

The color developer used in the present invention preferably has a pH of 10 or more, and more preferably has a pH of 1 or more as described above.
0.2 to 11.5, and the color developer may further contain a compound of a known developer component. In order to maintain the above pH, it is preferable to use various buffers. Examples of the buffer 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 salt, valine salt,
Proline salts, trishydroxyaminomethane salts, lysine salts and the like can be used. Especially carbonates, phosphates,
Tetraborate, hydroxybenzoate is soluble, pH 9.0
It has excellent buffering capacity in the above high pH range, has the advantage of being inexpensive without adverse effects on photographic performance (such as fogging) even when added to a color developer, and using these buffering agents. Particularly preferred.

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-
Potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. However, the invention is not limited to these compounds.
The amount of the buffer added to the color developer is preferably at least 0.1 mol / l, and particularly preferably from 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used in the color developing solution as an agent for preventing precipitation of calcium and magnesium, or for improving the stability of the color developing solution. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N,
N ', N'-tetramethylenesulfonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid Acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2
-Hydroxybenzyl) ethylenediamine-N, N'-
Examples thereof include diacetic acid and 1,2-dihydroxybenzene-4,6-disulfonic acid. These chelating agents may be used in combination of two or more as necessary. These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. For example, 0.1g ~ 10 per liter
g.

An optional development accelerator can be added to the color developer if necessary. As a development accelerator,
No. 6088, No. 37-5987, No. 38-7826, No. 44-12380,
Thioether compounds disclosed in JP-A Nos. 45-9919 and U.S. Pat.
-49829 and 50-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44
No. -30074, quaternary ammonium salts represented in JP-A-56-156826 and JP-A-52-43429, U.S. Pat.
Nos. 903, 3,128,182, 4,230,796, 3,253,91
No. 9, Japanese Patent Publication No. 41-11431, U.S. Pat.No. 2,482,546,
Amine compounds described in each gazette or specification such as 2,596,926 and 3,582,346, JP-B-37-16088, 42-252
No. 01, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41-11431,
42-23883 and U.S. Pat.No. 3,532,501 such as polyalkylene oxides and other 1-phenyl-3-pyrazolidones, imidazoles, etc.
Etc. can be added as needed.

In the treatment according to the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-
Nitrogen-containing hetero groups such as nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine Ring compounds can be given as typical examples.

The color developing solution applicable to the present invention includes:
It preferably contains a fluorescent whitening agent. As the fluorescent whitening agent, the 4,4'-diamino-2,2'-disulfostilbene compounds shown above are preferable. Further, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as needed.

The processing temperature of the color developing solution applicable to the present invention is preferably 30 ° C. or higher, more preferably 40 to 5 ° C.
The temperature is 5 ° C, particularly preferably 40 to 50 ° C. The processing time is preferably 90 seconds or less, more preferably 5 to 6 seconds.
0 seconds, more preferably 5 seconds to 30 seconds. It is preferable that the replenishing amount is small, but 20 to 60 per m ^{2 of} the light-sensitive material.
0 ml is suitable, preferably 30 to 120 ml, particularly preferably 15 to 60 ml.

After the development step, processing with a bleaching solution, a bleach-fixing solution and a fixing solution is performed. In the present invention, the bleaching solution and the bleach-fixing solution which are the desilvering bath (desilvering solution) contain at least the compound of the formula (I) described in JP-A-8-304980, preferably a stilbene-based fluorescent brightener. including. In the present invention, as the bleaching agent used in the bleaching solution or the bleach-fixing solution, any bleaching agent can be used. Particularly, organic complex salts of iron (III) (for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) can be used. Acids, complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; and hydrogen peroxide.

Of these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Iron (III)
Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylene Diaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol etherdiaminetetraacetic acid, beta-alanine diethylenediamine N, N'-disuccinic acid, alpha methyl nitrilotriacetic acid, ethylenediamine N, N '-Disuccinic acid, 1,3 diaminopropane N,
N'-disuccinic acid, ethylenediamine N, N'-dimalonic acid, 1,3 diaminopropane N, N'-dimalonic acid and the like can be mentioned. These compounds may be any of the sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodiacetic acid, ethylenediamine N, N′-disuccinic acid, 1,3 diaminopropane N, Iron (III) complex salts of N'-disuccinic acid and ethylenediamine N, N'-dimalonic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc., to form a ferric ion complex salt in a solution. Also,
The chelating agent may be used in excess of forming a ferric ion complex salt. Among the iron complexes, iron aminopolycarboxylate complexes are preferred, and the amount of addition is 0.01 to 1.0 mol / l, preferably 0.05 to 0.50 mol / l, and more preferably 0.10 to 0 mol / l. .50 mol / l, more preferably 0.15 to 0.40 mol / l.

Various compounds can be used as a bleaching accelerator in the bleaching solution, bleach-fixing solution and / or prebath thereof. For example, U.S. Patent No. 3,893,858, German Patent No. 1,290,812, JP-A-53-95630, Research Disclosure No. 17129 (July 1978)
Compounds having a mercapto group or a disulfide bond described in JP-B-45-8506 and JP-A-52-20832.
And thiourea compounds described in U.S. Pat. No. 3,706,561 or halides such as iodine and bromide ions are preferred in terms of excellent bleaching power. Other bleaching solutions or bleach-fixing solutions applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodine. A rehalogenating agent such as an iodide (eg, ammonium iodide). Borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid,
Addition of one or more inorganic acids and organic acids having pH buffering capacity such as phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate, guanidine, etc. can do.

The fixing agent used in the bleach-fixing solution or the fixing solution is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Ethylenebisthioglycolic acid, 3,6-dithia-1,
Thioether compounds such as 8-octanediol and water-soluble silver halide dissolving agents such as thioureas;
These can be used alone or in combination of two or more. Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per liter is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or fixing solution used in the present invention is preferably from 3 to 8, more preferably from 4 to 7. When the pH is lower than this, the desilverability is improved, but the deterioration of the solution and the leuco formation of the cyan dye are promoted. Conversely p
If H is higher than this, desilvering will be delayed and stain will easily occur. The pH range of the bleaching solution used in the present invention is 8 or less, preferably 2 to 7, and particularly preferably 2 to 6.
If the pH is lower than this, the deterioration of the solution and the leuco conversion of the cyan dye are promoted, and if the pH is higher than this, desilvering is delayed,
Stain is likely to occur. To adjust the pH,
If necessary, hydrochloric acid, sulfuric acid, nitric acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added.

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, defoaming agents or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. The bleach-fixing solution and the fixing solution include sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives, It preferably contains a sulfite ion releasing compound such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are converted to sulfite ions
It is preferable to contain 0.02 to 1.0 mol / liter,
More preferably, it is 0.04 to 0.6 mol / liter.

As a preservative, sulfite is generally added, but other additives such as ascorbic acid and carbonyl bisulfite, or a carbonyl compound may be added. Furthermore, buffers, optical brighteners, chelating agents, defoamers,
A fungicide may be added as desired. The processing time of the bleach-fixing process according to the present invention is 5 seconds to 120 seconds, preferably 10 seconds to 60 seconds, and particularly preferably 20 seconds or less. The processing temperature is 25 ° C to 60 ° C, preferably 30 ° C to 5 ° C.
0 ° C. The replenishment rate is 20 per m ² of photosensitive material.
ml to 250 ml, preferably 30 ml to 100 ml,
Particularly preferably, the volume is 15 ml to 60 ml.

After desilvering such as fixing or bleach-fixing, washing and / or stabilization are generally performed. The amount of rinsing water in the rinsing step can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (the number of stages), and various other conditions.
Among them, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in Journal of the Society of Motion Picture and Television Engineers (Journal of the Society of Motion Picture).
and Television Engineers) Vol. 64, pp. 248-253 (1955
May issue). Usually, the number of stages in the multistage countercurrent system is preferably 3 to 15, and particularly preferably 3 to 10. Fig. 1 from the viewpoint of speeding up and miniaturization
It is preferable to sequentially pass through the washing tank as described in (1).
That is, during the washing and / or stabilizing step, the photosensitive material is not exposed to the liquid surface or the outside air, so that the washing and / or stabilizing treatment can be achieved efficiently and in a short time.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, 500 ml or less per 1 m ^{2 of the} photosensitive material. However, bacteria increase due to an increase in the residence time of water in the tank. In addition, there arises a problem that the generated suspended matter adheres to the photosensitive material. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, and
Chlorinated fungicides such as chlorinated sodium isocyanurate described in JP-120145, benzotriazole, copper ions described in JP-A-61-26761, and others, "Humiguchi Higaku's" Bactericidal and Fungicide Chemistry "( 1986) Sankyo Publishing, Sanitary Technology Society,
"Microbial disinfection, sterilization, and fungicide technology" (1982) Industrial Technology Association, Japan Society of Fungicide and Fungicide, "Encyclopedia of Fungicide and Fungicide" (1986)
) Can also be used.

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used. Continue with the above washing process or
Alternatively, the treatment can be performed directly with the stabilizing solution without going through the washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound typified by formalin, a buffer for adjusting the membrane pH to a level suitable for dye stabilization, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, a fluorescent whitening agent and a hardening agent may be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly performed without going through a washing step, a known method described in JP-A-57-8543, JP-A-58-14834, JP-A-60-220345 and the like can be used. Can all be used. In addition, it is also a preferable embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering treatment. The preferred pH of the washing step or the stabilizing step is 4 to 10, and more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally 20 ° C to 50 ° C, preferably 25 ° C to 45 ° C. The time can be set arbitrarily, but a shorter time is desirable from the viewpoint of reducing the processing time. Preferably it is 10 seconds to 60 seconds, more preferably 15 seconds to 45 seconds. It is preferable that the replenishing amount is small in view of running cost, reduction of discharge amount, handleability, and the like. A specific preferable replenishing amount is 0.5 to 50 times, preferably 3 to 40 times the carry-in amount from the previous bath per unit area of the photosensitive material.
Alternatively, the amount is 500 ml or less, preferably 300 ml or less per m ^{2 of the} photosensitive material. Replenishment may be performed continuously or intermittently. The liquid used in the water washing and / or stabilizing step can be further used in the previous step. As an example of this, the overflow of the washing water reduced by the multi-stage countercurrent method is caused to flow into a bleach-fix bath preceding the bath, and the bleach-fix bath is replenished with a concentrated solution to reduce the amount of waste liquid.

As the stirring of each processing tank used in the present invention, a well-known method such as a method of spraying a liquid, a method using mechanical stirring or an ultrasonic wave can be used. In particular, a method which directly affects the surface of the photosensitive material is preferable.
No. 58, Japanese Patent Application Laid-Open No. 4-145434, and the like, a method of using jet agitation or utilizing pressure at the time of passage between a pair of rollers can be used. A supplementary description is given of the drying process that can be used in the present invention. The drying time for completing the image by the processing of the present invention is also preferably 5 seconds to 20 seconds.

As the method of developing the photosensitive material of the present invention after exposure, there are a conventional method of developing with a developing solution containing an alkali agent and a developing agent, and an alkaline solution containing a developing agent in the photosensitive material and containing no developing agent. The method can also be applied to a wet process such as a method of developing with an activator solution. In particular, the activator method is a method that does not include a developing agent in the processing solution and has a small load when processing the waste liquid, and is a preferable method from the viewpoint of environmental protection. In the activator method, examples of a developing agent or a precursor thereof incorporated in a photosensitive material include, for example, JP-A-8-234388 and JP-A-9-15269.
2, JP-A-9-152693, JP-A-9-1601
The hydrazine-type compound described in No. 93 is preferred.

Further, a development method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, Japanese Patent Application Laid-Open
An image forming method using an activator liquid containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152699 is preferably used. In the activator method, after processing with an activator solution, desilvering is usually performed.However, in an image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted, and a simple method such as washing with water or stabilizing process can be performed. Further, in a method in which image information is read from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photography is used.

As the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention, known materials and processing methods can be used. Preferably, Research Disclosure Item 36544 (1994)
Sep., pp. 536-541 and JP-A-8-23438.
No. 8 can be used.

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to this. Example 1 After a corona discharge treatment was applied to the surface of a support obtained by coating both sides of a paper with a polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and further a first layer to a seventh layer Were sequentially coated to prepare a sample (101) of a silver halide color photographic light-sensitive material having the following layer structure. The coating solution for each photographic constituent layer was prepared as follows. The average particle size shown below means the average value of the diameter of the particle area measured by the so-called projection area method.

Preparation of Coating Solution for Fifth Layer 300 g of cyan coupler (ExC-1), 250 g of color image stabilizer (Cpd-1), 1 color image stabilizer (Cpd-8)
0 g, color image stabilizer (Cpd-9) 10 g, color image stabilizer (Cpd-11) 20 g, ultraviolet absorber (UV-1) 1
4 g, UV absorber (UV-2) 50 g, UV absorber (UV-3) 40 g and UV absorber (UV-4) 6
0 g was dissolved in 230 g of a solvent (Solv-6) and 350 ml of ethyl acetate, and this solution was emulsified and dispersed in 6500 g of a 10% aqueous gelatin solution containing 200 ml of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion C. On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 mixture of large-sized emulsion C having an average grain size of 0.50 μm and small-sized emulsion C having an average grain size of 0441 μm (silver molar ratio). 0.09 and 0.11 in each of the emulsions, in which 0.5 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grains. In this emulsion, red-sensitive sensitizing dyes G and H shown below were mixed with silver 1
Per mole, 6.0 × for large size emulsion C
10 ^-5 mol, and 9.0 × 10 ^-5 mol for small-size emulsion C, respectively. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a fifth layer coating solution having the composition described below. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Ab-1, Ab-2 , Ab-3 and Ab-4 the total amount respectively 15.0 mg / m ² in each layer, 60.0mg / m ^2,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

[0183]

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The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0185]

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(Sensitizing dyes A, B and C were used in an amount of 1.4.times.
^10-4 moles, ^1.7x each for small size emulsions
10 ^-4 mol was added. Green sensitive emulsion layer

[0187]

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(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMol of sensitizing dye F per mol of silver halide.
2.0 × 10 for large emulsions^-FourMole, small
2.8 × 10 for size emulsion^-FourMole was added. ) Red-sensitive emulsion layer

[0189]

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(Sensitizing dyes G and H were converted to silver halide 1
6.0 × 1 per mole for large size emulsions
0 ^-5 mol, respectively 9.0 × 1 to the small size emulsion
0 ^-5 mol was added. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide. )

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Further, a blue-sensitive emulsion layer, a green-sensitive emulsion layer and
1- (3-methylureidophenyl) was added to the red-sensitive emulsion layer.
) -5-mercaptotetrazole
3.3 × 10 per mole of silver halide^-FourMol, 1.0 × 10^-3
Mol and 5.9 × 10^-FourMole was added. Furthermore, the second
Layer, the fourth layer, the sixth layer and the seventh layer, respectively.
mg / m ^Two 0.2 mg / m^Two , 0.6 mg / m^Two ,
0.1mg / m^Two Was added so that Blue sensitivity
4-hydroxy-6 to the emulsion layer and the green-sensitive emulsion layer
-Methyl-1,3,3a, 7-tetrazaindene
1 × 10 per mol of silver halide^-FourMole, 2
× 10^-FourMole was added. Also, methacrylate is added to the red-sensitive emulsion layer.
Copolymer of phosphoric acid and butyl acrylate (weight ratio 1: 1, flat
Average molecular weight of 200,000 to 400,000) is added to 0.05 g /
m2 was added. In addition, the second, fourth and sixth layers
Catechol-3,5-disulfonate disodium
6mg / m each^Two, 6mg / m^Two, 18mg / m^TwoBecomes
Was added as follows. Also, to prevent irradiation
In addition, the following dyes are shown in the emulsion layer
Was added.

[0193]

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content of 16% by weight, ZnO; content of 4% by weight) and a fluorescent whitening agent (4,4'-bis (benzoxazolyl) stilbene and 4,4-bis (5-methylbenzoxazolyl) stilbene) 8/2 (weight ratio): 0.05% by weight), including bluish dye (ultramarine)

First Layer (Blue-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large-size emulsion A with an average grain size of 0.72 μm and small-size emulsion A with a 0.60 μm emulsion (silver molar ratio The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. ) 0.26 Gelatin 1.35 Yellow coupler (ExY) 0.62 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0 .08 Solvent (Solv-1) 0.23

Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.45 μm and small-size emulsion B having a 0.35 μm size (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-1) 0.05 UV absorber (UV-2) 0.03 UV absorber (UV-3) 0.02 UV absorption Agent (UV-4) 0.04 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 0.002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer ( Cpd-7) 0.02 Color image stabilizer (Cpd-8) 0.03 Image stabilizer (Cpd-9) 0.01 Color Image Stabilizer (Cpd-10) 0.0001 solvent (Solv-3) 0.11 solvent (Solv-4) 0.22 solvent (Solv-5) 0.20

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention agent (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large emulsion C having an average grain size of 0.50 μm and small emulsion C of 0.41 μm (silver mole) The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.20 Gelatin 1.11 Cyan coupler (ExC-1) 0.30 Ultraviolet absorber (UV-1) 0.14 Ultraviolet absorber (UV-2) 0.05 Ultraviolet absorber (UV-3) 0.04 UV absorber (UV-4) 0.06 Color image stabilizer (Cpd-1) 0.25 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer Agent (Cpd-11) 0.02 Solvent (Solv-6) 0.23

Sixth layer (UV absorbing layer) Gelatin 0.66 UV absorbing agent (UV-1) 0.19 UV absorbing agent (UV-2) 0.06 UV absorbing agent (UV-3) 0.06 UV absorbing Agent (UV-4) 0.05 Ultraviolet absorber (UV-5) 0.09 Solvent (Solv-7) 0.25

Seventh layer (protective layer) Gelatin 1.00 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-12) 0.01

[0202]

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[0203]

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[0204]

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[0205]

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[0206]

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[0207]

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[0208]

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[0209]

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[0210]

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(Sample 102) In the silver halide color photographic light-sensitive material 101 produced as described above, 70 mol% of the cyan coupler Exc-1 having the composition of the fifth layer was added to the pyrrolotriazole coupler (1) according to the present invention. Sample 1 in which the compound (52) of the general formula (III) according to the present invention was added to each of the second, fourth and fifth layers in the following manner.
02 was produced.

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large-size emulsion C having an average grain size of 0.50 μm and small-size emulsion C of 0.41 μm (silver mole The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.8 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.12 Gelatin 1.11 Cyan coupler (1) 0.21 Cyan coupler (ExC-1) 0.09 Color image stabilizer (Cpd-1) 0.05 Color image stabilizer (Cpd-6) 0.05 Formula (III) color mixture inhibitor (52) 0.01 Color image stabilizer (Cpd-8) 0.04 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-13) 0.01 color Image stabilizer (Cpd-14) 0.06 Color image stabilizer (Cpd-15) 0.0. 9 Color image stabilizer (Cpd-16) 0.09 Color image stabilizer (Cpd-17) 0.01 Solvent (Solv-5) 0.15 Solvent (Solv-8) 0.05 Solvent (Solv-9) 0 .10

(Samples 103 to 108) Further, with respect to the silver halide color photographic light-sensitive material 102 prepared as described above, the pyrrolotriazole coupler (1) in the fifth layer was added in an equimolar amount as shown in Table 3. And a second layer, a fourth layer and a fifth layer of the color mixing inhibitor (compound (52)) of the general formula (III) according to the present invention (compound (52)) were added to each layer in an amount of 0.01 as shown in Table 3. Sample 1 with or without addition
Nos. 03 to 108 were produced.

The sample 102 described above was subjected to a color temperature of 3200K.
, A continuous-tone wedge exposure is performed, and a running process (accumulated replenishment amount of the developing tank is performed) using a processing apparatus having the configuration shown in FIG. (Until three times the volume). The purpose of the running process is to bring the liquid in the processing machine into a steady state, that is, to adjust conditions for a test described later. Exposure at this time is 25 seconds with an exposure time of 0.1 second.
The exposure was performed so that the exposure amount was 0 CMS. Processing process temperature Time replenisher ^* Tank capacity Color development 45 ° C 22 seconds 35 ml 6.0 liter Bleach-fix 40 ° C 15 seconds 35 ml 4.0 liter Rinse 40 ° C 3 seconds-1.7 liter Rinse 40 ° C 3 seconds -1 .2 liters rinse 40 ° C. 3 seconds - 1300 liters rinse 40 ° C. 3 seconds - 1300 liters rinse 40 ° C. 6 seconds 70 ml 1.7 liter drying 85 ° C. 10 seconds * replenishment rate amount per photosensitive material 1 m ² Expressed by

[0215] Each tank was sprayed with a fountain flow perpendicular to the sample surface. The spray rate was 3.0 liter / min. The water washing process was a countercurrent system with five tanks. Reverse osmosis membrane is a spiral type RO manufactured by Daicel Chemical Industries.
Module element DRA-80 (effective membrane area 1.1
m ² , a polysulfone-based composite membrane) was mounted on a plastic pressure-resistant vessel PV-0321 manufactured by the same company. The reverse osmosis membrane was installed as shown in FIG. 1, and a liquid was sent to the reverse osmosis membrane using a pump at a pressure of 7 kg / cm ² and a flow rate of 1.8.
At a rate of 1 liter / min, the water in the fourth rinse tank was pumped, the permeated water was supplied to the fifth rinse tank, and the concentrated water was returned to the fourth rinse tank. The amount of permeated water to the fifth tank is 2
It was 50-400 ml / min. In the drying process, the heat rollers 14A and 16A shown in FIG. 1 were set at 90 ° C., the hot air temperature was 85 ° C., and the mass velocity of the hot air blown per unit area of the heat receiving surface of the photosensitive material was 2000 kg / m ² · hr. still,
The mass velocity (G) is represented by the following equation. G = ρ · Af · v · 3600 [ρ: density of hot air (kg / m ³ ), Af: nozzle opening ratio (ratio of total opening area of nozzle provided per unit area of heat receiving surface), v: Hot air velocity (m / s)]

The composition of each processing solution is as follows. Color developer Tank solution Replenisher Water 800ml 800ml Triethanolamine 12.0g 12.0g Ethylenediaminetetraacetate 3.0g 3.0g Disodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5g 0.5g 0.5g Potassium chloride 15.8 g ----Potassium bromide 0.045 g --- 2,2 ', 6,6'-tetrasodium sulfonatoethyl-4,4'-triazinylaminostilbene-2,2 Sodium '-disulfonate 5.0 g 8.0 g sodium sulfite 0.05 g 0.1 g disodium-N, N-bis (sulfonateethyl) hydroxylamine 10.0 g 14.0 g N-ethyl-N- (β-methane Sulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 6.0 g 18 Potassium 5g carbonate 26.3 g 26.3 g Water to make (adjusted with 25 ° C. / potassium hydroxide) 1000 ml 1000 ml pH to 10.35 12.80

Bleach-fixing solution Tank solution Replenisher Water 500 ml 500 ml Ammonium thiosulfate (75%) 80 ml 160 ml Ethylenediaminetetraacetic acid 4.4 g 8.0 g Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate 62.0 g 124.0 g ammonium sulfite Monohydrate 58.0 g 116.0 g Ammonium bromide 10.0 g 20.0 g n-butylguanidine 1/2 sulfate 6.6 g 14.8 g Acetic acid (50%) 66.0 ml 132.0 ml Nitric acid (67%) ) 18.29 g 36.58 g Water is added to 1000 ml 1000 ml pH (25 ° C: adjusted with nitric acid) 5.00 4.80

Rinse solution (tank solution and replenisher are the same) Deionized water (calcium and magnesium are each 3 ppm
Less than)

After completion of the running process, samples 101 to 10
6, a sensitometer (Fuji Photo Film Co., Ltd., FW type, light source color temperature 3200K, exposure time 0.1 second, exposure amount 25
0CMS), exposure is performed through gradation exposure of a three-color separation filter for sensitometry, development is performed, and the density change of the developed sample during storage is measured by the method described below. did. Since the density change takes the form of an increase in the density, it may be referred to as color increase over time.

(Evaluation of color increase over time) The density of the sample (for sensitometry) immediately after the development processing was measured, and the highest density portion (Dmax) measured with red light (filter light equivalent to status A) was determined from the characteristic curve. I read.
Next, the sample after measurement was stored under the following conditions, and Dmax after aging was measured in the same manner. Then, the time-dependent color increase of the cyan dye was determined as described below. -Storage conditions: 40 ° C, 70% relative humidity, 1 day-Color increase over time (ΔDmax (R)) = (Dmax (R) after storage)-
(Dmax (R) before storage) Table 3 shows the results obtained by the above method.

[0221]

[Table 3]

As can be seen from Table 3, the color photographic material containing the pyrrolotriazole coupler of the general formula (I), which is an embodiment of the present invention, is developed by a method employing the above drying conditions. It can be seen that the increase in the density of the cyan dye image due to the subsequent aging is suppressed. It has also been found that the effect of suppressing the increase in density over time can be further enhanced by further incorporating the color mixture inhibitor of the general formula (III) of the present invention into the light-sensitive material. When the coupler for comparison was used, the density of the cyan dye image increased with the elapse of time after the development processing, and the effect of adding the color mixture inhibitor of the general formula (III) was not observed.

Example 2 The same procedure as in Example 1 was performed except that the samples 102 and 108 described in Example 1 of the present application were subjected to continuous tone wedge exposure at a color temperature of 3200 K, and the drying conditions were changed as shown in Table 4. And the increase in concentration over time was determined. Table 4 shows the results
Shown in

[0224]

[Table 4]

As is apparent from Table 4, when the color photographic material containing the pyrrolotriazole coupler of the general formula (I) according to the embodiment of the present invention is subjected to development processing, it is dried under the drying conditions according to the embodiment of the present invention. It can be seen that the increase in concentration over time is suppressed. In the case of Sample 108 using the coupler for comparison, even when air drying under the conditions of the present invention was performed, the density of the cyan dye image increased over time after the development processing, and the effect of the invention was not recognized. Needless to say, in Tables 3 and 4, the term "time-dependent color increase" is a term meaning an increase in density over time after the development processing.

[0226]

When a silver halide color light-sensitive material using a pyrrolotriazole type cyan coupler is subjected to development processing, the drying step is performed by contact heating with a heat roller, and further, hot air is blown from a nozzle or a hole at a mass velocity of 10 or more.
By adopting a drying method in which the photosensitive material surface is applied at a pressure of at least 00 kg / m ² · hr, the density of the cyan dye is prevented from increasing with time, and the image after development is stabilized.
When the light-sensitive material contains a 3-pyrazolidone derivative represented by the formula (III) in addition to the cyan coupler, the effect becomes more remarkable.

[Brief description of the drawings]

FIG. 1 is a schematic view showing one embodiment of a developing machine for silver halide photographic color paper to which the present invention is applied.

FIG. 2 is a cross-sectional view in a direction orthogonal to the direction in which the photographic paper is transported in the drying unit shown in FIG.

FIG. 3 is a plan view showing the vicinity of a chamber of a drying unit shown in FIG. 1;

FIG. 4 is an enlarged sectional view of a chamber and a belt in a first half of a drying unit according to another embodiment of the present invention.

FIG. 5 is a plan view of the chamber shown in FIG.

FIG. 6 is an explanatory diagram showing a dimensional relationship of holes.

[Explanation of symbols]

 7 Drying Unit (Photosensitive Material Drying Device) 11 Photographic Paper (Photosensitive Material) 14 Transport Roller Pair 14A Heat Roller 16 Transport Roller Pair 16A Heat Roller 20 Belt Conveyor 28 Belt 28A Belt Linear Section 30 Belt Transport Roller 31 Belt Transport Roller 32 Drying Chamber 34 Plate Material (Perforated Plate) 54 Heater 66 Hot Air Temperature Control Sensor 68 Round Pipe (Nozzle Group) 90 Reverse Osmosis Device 91 Tension Roller 93 Nozzle 94 Blade

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having at least a cyan-color-forming photosensitive silver halide emulsion layer and a non-color-forming and non-photosensitive hydrophilic colloid layer on a support, followed by color development. In a processing method of sequentially performing processing of each step of desilvering, washing and / or stabilizing, and drying,
(I) at least one of the cyan-color-forming photosensitive silver halide emulsion layers contains at least one cyan dye-forming coupler selected from compounds represented by the following general formula (I); In the drying step, after the photosensitive material is contact-heated by a heat roller, the photosensitive material is blown dry by warm air blown from the perforated plate or the nozzle group toward the photosensitive material, and (3) in the blow drying,
A method for processing a silver halide color photographic light-sensitive material, wherein the mass velocity of hot air blown per unit area of the heat-receiving surface of the light-sensitive material is 1000 kg / m ² · hr or more. Embedded image Wherein (I), Z ^a, respectively Z ^b is -C (R ³⁾ = or represents -N =. However, either Z ^a or Z ^b is −
Is N =, the other is -C (R ³⁾ is =. R ¹ and R
² has a Hammett's substituent constant σ _p value of 0.20
It represents the above electron withdrawing group, and the sum of the σ _p values of R ¹ and R ² is 0.65 or more. R ³ represents a hydrogen atom or a substituent. X represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of a color developing agent. R
^{The group of 1} , R ² , R ^3, or X may be a divalent group and form a homopolymer or a copolymer by bonding to a dimer or higher polymer or a polymer chain. 2. A silver halide color photographic light-sensitive material according to the following general formula (III), wherein one or both of a photosensitive silver halide emulsion layer having a cyan coloring property and a hydrophilic colloid layer having a non-coloring and non-photosensitive property are provided. 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, which contains at least one of the compounds represented by the formula (1). Embedded image In formula (III), R ^a1 and R ^a2 each independently represent a hydrogen atom, an alkyl group or an aryl group. R ^a3 and R ^a4 represent a hydrogen atom, an alkyl group or an aryl group. R ^a5 represents an aryl group. However, ^Ra1 , ^Ra2 , ^Ra3 , ^Ra4
And the total number of carbon atoms of ^Ra5 does not become 13 or less.