JPH05158202A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce variation of photographic characteristics, to ensure sufficient color development performance, and to obtain the photographic characteristics small in fog even at the time of using a contaminated developing solution by incorporating at least one kind of specified cyan coupler in a red-sensitive emulsion layer composing the photosensitive material and developing the photosensitive material with a color developing solution containing a specified amount of chlorine ions or more. CONSTITUTION:The red-sensitive silver halide emulsion layer composing the photosensitive material contains at least one of the pyrrolotriazole type cyan couplers represented by formula I or II and the color developing solution to be used contains the chlorine ions in a concentration of >=0.08mol/l. In formulae I and II, one of Za and Zb is -N= and the other is -C(R3)=; each of R1 and R2 is an electron attractive group having a Hammett's substituent constant sigmaP of >=0.20, and the sum of the Hammett's substituent constant of both is >=0.65: R3 is H or a substituent; and X is H or a group to be released by coupling with the oxidation product of an aromatic primary amine color developing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a processing method for obtaining excellent photographic characteristics of high maximum density with less fog in rapid processing, and more stable photographic characteristics. On how you can maintain.

[0002]

2. Description of the Related Art In a method of processing a silver halide color photographic light-sensitive material, a technique using a high silver chloride emulsion is used for the purpose of shortening processing time and reducing pollution.
And Japanese Patent Application Laid-Open No. 61-70552. Indeed, when a high silver chloride emulsion is used, the processing time is shortened, but conversely, the photographic characteristics fluctuate greatly with changes in the pH of the color developer and changes in the concentration of the main agent, and on the low activity side. Particularly, when the sensitivity of cyan is lowered, and further, when the bleach-fix solution is mixed (contaminated) with the color developing solution, remarkable fog of cyan occurs, and a solution has been desired.

Further, Japanese Patent Application Laid-Open No. 63-106655 and Japanese Patent Application Laid-Open No. 1-116639 disclose a technique of processing a high silver chloride light-sensitive material with a color developing solution containing a high concentration of chlorine ions. , When the chloride ion concentration increases,
Particularly in rapid processing, the photographic characteristics fluctuate greatly and stable performance cannot be obtained.

Further, a pyrrolotriazole type coupler is described in JP-A-62-279339 and is disclosed as a magenta coupler excellent in color reproduction and image storability. However, the problems as described in the present invention have not been pointed out, and there has been no technical disclosure as a cyan coupler, and the effect of the present invention cannot be analogized at all.

[0005]

SUMMARY OF THE INVENTION Therefore, the present invention provides a processing method capable of obtaining stable photographic characteristics with little photographic fluctuation and sufficient color development in rapid processing, and with less fogging even when contaminated. To do.

[0006]

It has been found that the above objects can be achieved by using the following techniques. That is, (1) in a method of subjecting an exposed halogenated color photographic light-sensitive material to color development and desilvering, the red-sensitive emulsion layer constituting the light-sensitive material is provided with a pyrrolo formula represented by the following general formula (I) or (II). A method for processing a silver halide color photographic light-sensitive material, which comprises using a color developing solution containing at least one triazole-based cyan coupler and performing color development with a chlorine ion content of 0.08 mol / liter or more.

[0007]

[Chemical 2]

(In the formula, Za and Zb are each -C (R
₃ ) = or-N =. However, one of Za and Zb is -N =, the other is -C (R ₃₎ is =. R ₁
And R ₂ each have a Hammett substituent constant σ _p value of 0.
Represents 20 or more electron-withdrawing groups, and σ of R ₁ and R ₂
The sum of _p- values is 0.65 or more. R ₃ represents a hydrogen atom or a substituent. X represents a hydrogen atom or a group capable of splitting off in a coupling reaction with an oxidation product of an aromatic primary amine color developing agent. The group of R ₁ , R ₂ , R ₃ or X may be a divalent group and may be bonded to a dimer or higher polymer or a polymer chain to form a homopolymer or a copolymer. (2) The silver halide color photographic light-sensitive material as described in (1) above, wherein the silver halide color photographic light-sensitive material contains at least one layer of a high silver chloride emulsion containing 90 mol% or more of chlorine ions. Processing method. (3) The method for processing a silver halide color photographic light-sensitive material as described in (1) above, wherein the color development is carried out for 50 seconds or less and 36 ° C. or more.

The cyan coupler of the present invention will be described in detail below. Za and Zb each -C (R ₃₎ = or represent -N =. However, one of Za and Zb is -N =, the other is -C (R ₃₎ is =. That is, the cyan coupler of the present invention is specifically represented by the following general formula (I-
It is represented by a), (Ib), (II-a) and (II-b).

[0010]

[Chemical 3]

[0011]

[Chemical 4]

(In the formula, R ₁ , R ₂ , R ₃ and X have the same meanings as in formula (I) or (II), respectively.)

R ₃ represents a hydrogen atom or a substituent, and the substituent is 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 or 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 thereof include phosphonyl group, aryloxycarbonyl group, acyl group and azolyl group. These groups may be further substituted with the substituents exemplified for R ₃ .

More specifically, R ₃ is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group). , An alkynyl group, a cycloalkyl group, a cycloalkenyl group, and more specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-Pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (eg phenyl, 4-t-butylphenyl, 2,4-di-t-amyl) Phenyl, 4-tetradecanamidophenyl), a heterocyclic group (for example, 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-butyl). Phenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3
-Methoxycarbamoyl), an acylamino group (for example,
Acetamide, benzamide, tetradecanamide, 2
-(2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino A group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino),
Anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino,
2-chloro-5-dodecyloxycarbonylanilino,
N-acetylanilino, 2-chloro-5- {2- (3-
t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoyl) Amino, 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), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 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 group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl) , Dodecyloxycarbonyl, octadecyloxycarbonyl), a heterocyclic oxy group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pi). Valoylaminophenylazo,
2-hydroxy-4-propanoylphenylazo), acyloxy group (eg acetoxy), carbamoyloxy group (eg N-methylcarbamoyloxy, N-
Phenylcarbamoyloxy), silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (eg,
Phenoxycarbonylamino), imide group (eg, N
-Succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2-
Benzothiazolylthio, 2,4-di-phenoxy-1,
3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl) , Phenylphosphonyl), an aryloxycarbonyl group (for example, phenoxycarbonyl), an acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), an azolyl group (for example, imidazolyl, pyrazolyl, 3- Chloro-pyrazol-1-yl, triazolyl).

R ₃ is preferably an alkyl group, aryl group, heterocyclic group, cyano group, nitro group, acylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, 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, An azolyl group can be mentioned.

More preferably, it is an alkyl group or an aryl group, more preferably an alkyl group or an aryl group having at least one substituent, and more preferably at least one alkoxy group or a sulfonyl group from the viewpoint of cohesiveness. , An alkyl group or an aryl group having a sulfamoyl group, a carbamoyl group, an acylamide group or a sulfonamide group as a substituent. Particularly preferred is an alkyl group or an aryl group having at least one acylamide group or sulfonamide group as a substituent. When the aryl group has these substituents, it is more preferable that they have at least the ortho position.

In the cyan coupler of the present invention, both R ₁ and R ₂ are electron withdrawing groups of 0.20 or more, and R ₁ is R _1.
When the sum of the σ _p values of R ₂ and R ₂ is 0.65 or more, color is developed as a cyan image. 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 1.8.

R ₁ and R ₂ are Hammett's substituent constants σ p
It is 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. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives in 1935 L. et al. P. A rule of thumb put forward by Hammett, which is widely accepted today. Substituent constants determined by Hammett's law include σ _p values and σ _m values, and these values are described in many general textbooks. A. Dean ed. "Lange's H
and book of Chemistry ", 12th Edition, 1979 (McGra
w-Hill) and "Special Issue on Chemistry", No. 122, 96-10
Details on page 3, 1979 (Nankodo). In the present invention, R ₁ and R ₂ are defined by the Hammett's substituent constant σ _p value, but it does not mean that the values known from the literatures described in these publications are limited only to certain substituents, and their values are It is needless to say that even if the document is unknown, it is included as long as it is included in the range when measured based on Hammett's rule.

Specific examples of R ₁ and R ₂ which are electron withdrawing groups having a σ _p value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, Nitro group, dialkylphosphono group, diarphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, Halogenated alkyl group, halogenated alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, aryl group substituted with another electron-withdrawing group having a σ _{p of} 0.20 or more, heterocyclic group , Halogen atom, azo group, or sel An example is a nonocyanate group. The group capable of further having a substituent among these substituents may further have a substituent as described for R ₃ .

[0020] 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, is)
o-butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), cyano group, nitro group, dialkylphosphono group (eg, dimethylphosphono), diarylphosphono Group (for example, diphenylphosphono), diarylphosphinyl group (for example, diphenylphosphinyl), alkylsulfinyl group (for example, 3-phenoxypropylsulfinyl), arylsulfinyl group (for example, 3-pentadecylphenylsulfinyl) ,
Alkylsulfonyl group (for example, methanesulfonyl, octanesulfonyl), arylsulfonyl group (for example,
Benzenesulfonyl, toluenesulfonyl), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy), acylthio group (eg, acetylthio,
Benzoylthio), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N
-Diethylsulfamoyl), a thiocyanate group, a thiocarbonyl group (for example, methylthiocarbonyl, phenylthiocarbonyl), a halogenated alkyl group (for example,
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-tetrafluoroethylthio), σ _p 0.20
An aryl group substituted with another electron-withdrawing group (for example, 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), a halogen atom (eg chlorine atom, bromine atom), an azo group (eg phenylazo) or a selenocyanate group. Among these substituents, a group which can further have a substituent is R ₃
It may further have a substituent such as those mentioned above.

Preferred as R ₁ and R ₂ are an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, Arylsulfonyl group, sulfamoyl group, halogenated alkyl group,
Halogenated alkyloxy group, halogenated alkylthio group, halogenated aryloxy group, two or more σ _p 0.
An aryl group substituted with 20 or more other electron-withdrawing groups,
And heterocyclic groups. More preferably,
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.

X represents a hydrogen atom or a group capable of splitting off in a coupling reaction with an oxidized product of an aromatic primary amine color developing agent. The splittable group is described in detail as a halogen atom, an alkoxy group or an aryloxy group. Group, acyloxy group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, 5 member or 6 Membered nitrogen-containing heterocyclic group, imide group, arylazo group, etc., and these groups may be further substituted with a group acceptable as a substituent for R ₃ .

More specifically, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, ethoxy, dothesyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryloxy. A group (for example, 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl. Sulfonyloxy groups (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (eg, dichloroacetylamino, heptafluorobutyrylamino), alkyl or aryl sulfonamide groups (eg, methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino), an alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryl Oxycarbonyl group (e.g., phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio group (e.g., dodecylthio,
1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, tetrazolylthio), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino),
5- or 6-membered nitrogen-containing heterocyclic group (for example, 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. In addition to these, X may take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. Further, X may contain a photographically useful group such as a development inhibitor or a development accelerator.

Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom. More preferable X
Is a halogen atom, an alkyl or arylthio group, and particularly preferably an arylthio group.

In the cyan coupler represented by the general formula (I) or (II), the group of R ₁ , R ₂ , R ₃ or X is a divalent group, and a dimer or higher polymer or polymer. It may combine with a chain to form a homopolymer or a copolymer. The homopolymer or copolymer bound to the polymer chain means an addition polymer having a cyan coupler residue represented by the general formula (I) or (II), a homopolymer or copolymer of an ethylenically unsaturated compound. This is a typical example. In this case, one or more kinds of cyan color-forming repeating units having a cyan coupler residue represented by the general formula (I) or (II) may be contained in the polymer, and a non-color-forming ethylene as a copolymer component. It may be a copolymer containing one type or two or more types of type monomers. The cyan color-forming repeating unit having a cyan coupler residue represented by the general formula (I) or (II) is preferably represented by the following general formula (P).

[0026]

[Chemical 5]

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-, -C.
OO- or a substituted or unsubstituted phenylene group, B represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, L represents -CONH-,
-NHCONH-, -NHCOO-, -NHCO-,-
OCONH-, -NH-, -COO-, -OCO-,-
CO -, - O -, - S -, - SO 2 -, - NHSO 2 -
Or it represents a -SO ₂ NH-. a, b, and c represent 0 or 1. Q represents a cyan coupler residue in which a hydrogen atom is removed from R ₁ , R ₂ , R ₃ or X of the compound represented by the general formula (I) or (II). As the polymer, a copolymer of a cyan color-forming monomer represented by the coupler unit of the general formula (I) or (II) and a non-color-forming ethylene-like monomer which is not coupled with an oxidation product of an aromatic primary amine developing agent is preferable.

As the non-color forming ethylene type monomer which does not couple with the oxidation product of the aromatic primary amine developing agent,
Acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid) An amide or ester derived from these acrylic acids (for example, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, dimethacrylate). Acetone acrylamide, 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 propio). 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-vinyl pyridine and 2- and -4
-Such as vinyl pyridine.

Acrylic acid esters, methacrylic acid esters and maleic acid esters are particularly preferred. Two or more kinds of non-color-forming ethylene type monomers used here can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer for copolymerization with the vinyl monomer corresponding to the above general formula (I) or (II) is the physical property of the copolymer formed. Properties and / or chemical properties, such as solubility, compatibility of the photographic colloid composition with binders such as gelatin, its flexibility, thermal stability, etc. can be selected to be favorably influenced.

In order to incorporate the cyan coupler of the present invention into a silver halide light-sensitive material, preferably in a red light-sensitive silver halide emulsion layer, it is preferable to use a so-called internal type coupler. For that purpose, R ₁ and R _At least one of R ₂ , R ₃ and X is a so-called ballast group (preferably having a total carbon number of 1).
It is preferably 0 or more), and more preferably 10 to 50 carbon atoms in total. It is particularly preferable that R ₃ has a ballast group. In the present invention, the general formula (I)
The cyan coupler represented by the formula (1) is preferable in terms of effect, and the cyan coupler represented by the general formula (Ia) is particularly preferable in terms of effect. Specific examples of the coupler of the present invention are shown below, but the present invention is not limited thereto.

[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

[Chemical 8]

[0035]

[Chemical 9]

[0036]

[Chemical 10]

[0037]

[Chemical 11]

[0038]

[Chemical 12]

[0039]

[Chemical 13]

[0040]

[Chemical 14]

[0041]

[Chemical 15]

[0042]

[Chemical 16]

[0043]

[Chemical 17]

[0044]

[Chemical 18]

[0045]

[Chemical 19]

[0046]

[Chemical 20]

[0047]

[Chemical 21]

[0048]

[Chemical formula 22]

Next, an example of synthesizing the cyan coupler of the present invention will be shown to explain the synthesizing method. Synthesis Example 1 (Synthesis of Exemplified Compound (1))

[0050]

[Chemical formula 23]

[0051]

[Chemical formula 24]

3-m-nitrophenyl-5-methylcyano-1,2,4-triazole (1) (20.0 g, 8
7.3 mmol) was dissolved in 150 ml of dimethylacetamide, and NaH (60% in oil) (7.3 g) was added little by little to it.
183 mmol) was added and heated to 80 ° C. Add 50 ml of ethyl bromopyruvate (13.1 ml, 105 mmol) to this.
The ml dimethylacetamide solution was slowly added dropwise. After dropping, the mixture was stirred at 80 ° C. for 30 minutes and cooled to room temperature. The reaction solution was acidified by adding 1N hydrochloric acid, extracted with ethyl acetate, dried with sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography to obtain 10.79 g (38%) of compound (2).

Reduced iron (9.26 g, 166 mmol) and ammonium chloride (0.89 g, 16.6 mmol) were suspended in 300 ml of isopropanol, and further 30 ml of water and concentrated hydrochloric acid (2 ml) were added.
ml was added, and the mixture was heated under reflux for 30 points. While heating under reflux
Compound (2) (10.79 g, 33.2 mmol) was added in small portions. After heating under reflux for 4 hours, the mixture was immediately filtered through Celite, and the filtrate was evaporated under reduced pressure. The residue was dissolved in a mixed solution of 40 ml of dimethylacetamide and 60 ml of ethyl acetate, compound (3) (25.6 g, 36.5 mmol) was added, and then triethylamine (23.1 ml, 166 mmol) was added, and the mixture was heated at 70 ° C. at 5 ° C. Heat for hours. The reaction solution was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with water and dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography to give compound (4) 1
6.5 g (52%) could be obtained.

Compound (4) (7.0 g, 7.30 mmol) was dissolved in 14 ml of isobutanol, tetraisopropyl orthotitanate (0.43 ml, 1.46 mmol) was added, and
Heated to reflux for hours. The reaction solution was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. After drying with sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 5.0 g (69%) of compound (5).

Compound (5) (5.0 g, 5.04 mmol) was dissolved in 50 ml of tetrahydrofuran and SO ₂ Cl ₂ was added under water cooling.
(0.40 ml, 5.04 mmol) was added dropwise, and after the addition, the mixture was stirred under water cooling for 4 hours. Water was added to the reaction solution, which was extracted with ethyl acetate, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography to obtain 3.9 g (76%) of Exemplified compound (1). Synthesis Example 2 (Exemplified compound (39))

[0056]

[Chemical 25]

36% of 2-amino-5-chloro-3,4-dicyanopyrrole (6) (6.78 g, 40.7 mmol)
38 ml of hydrochloric acid was added, and sodium nitrite (2.
A solution of 95 g, 42.7 mmol) in water (5.9 ml) was slowly added dropwise, and stirring was continued for 1.5 hours to synthesize a compound (7). To a solution prepared by adding 102 ml of 28% sodium methylate to a solution of compound (8) (9.58 g, 427 mmol) in 177 ml of ethanol under stirring with ice-cooling, slowly add the solution of compound (7) synthesized above under stirring with ice-cooling. Was added dropwise, and then stirring was continued for 1 hour. Then, the reaction solution was heated under reflux with stirring for 1.5 hours. Then, ethanol was distilled off from the reaction solution under reduced pressure, the residue was dissolved in chloroform, washed with saturated saline, dried over sodium sulfate, and then chloroform was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 4.19 g of compound (10) (2% from yield (6)).
9%).

The compound (6) was synthesized by chlorinating the 3,4-dicyanopyrrole, followed by nitration and iron reduction. In addition, the compound (8) was synthesized by a known method from γ-lactone and benzene.
From the “Journal of the American Chemical Society”
ciety), 76, 3209 (1954).

[0059]

[Chemical formula 26]

Powdered reduced iron (3.3 g, 59.0 mmol)
Water 10 ml, ammonium chloride (0.3 g, 5.9 mmo)
l) and acetic acid (0.34 ml, 5.9 mmol) were added and 1
After heating and refluxing stirring for 5 minutes, 31 ml of isopropanol was added, and the mixture was further heated and refluxed for 20 minutes with stirring. Next, (10) (4.
1 g, 11.8 mmol) in 14 ml of isopropanol was added dropwise, the mixture was heated under reflux with stirring for 2 hours, the reaction mixture was filtered using Celite as a filter aid, and the residue was washed with ethyl acetate.
The solution was evaporated under reduced pressure.

The residue was dissolved in a mixed solution of 16 ml of ethyl acetate and 24 ml of dimethylacetamide, and (11) (5.6 g,
13.0 mmol) was added, and triethylamine (8.2
ml, 59.0 mmol) was added, and the mixture was stirred at room temperature for 4 hours.
Water was added, the mixture was extracted with ethyl acetate, and the extract was washed with saturated saline. After drying with sodium sulfate, the solvent was distilled off under reduced pressure, the residue was purified by silica gel chromatography, and the exemplified compound (39)
Could be obtained 6.46 g (76%).

The light-sensitive material of the present invention may have at least one layer containing the cyan coupler of the present invention on the support, and as the layer containing the cyan coupler of the present invention,
Any hydrophilic colloid layer on the support may be used. A general light-sensitive material can be formed by coating at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer on a support in this order. However, the order may be different from this. Also, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned photosensitive emulsion layers. Color reproduction of the subtractive method is carried out by containing a silver halide emulsion having sensitivity in each wavelength range and a color coupler forming a dye having a complementary color relationship with the light to be exposed in these light-sensitive emulsion layers. be able to. However, the photosensitive emulsion layer and the coloring hue of the color coupler may not have the above correspondence. The cyan coupler of the present invention is preferably used as a main cyan coupler in the red-sensitive silver halide emulsion layer. The content layer of the cyan coupler of the present invention in the light-sensitive material is appropriately 1 × 10 ⁻³ to 1 mol, preferably 2 × 10 ⁻³ mol to 1 mol of silver halide.
It is 3 × 10 ⁻¹ mol.

The cyan coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, is dissolved in a high-boiling organic solvent (a low-boiling organic solvent is optionally used together), and is emulsified and dispersed in a gelatin aqueous solution to produce a halogen. The oil-in-water dispersion method of adding to a silver halide emulsion is preferred. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, steps of latex dispersion method as one of polymer dispersion methods, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) 2,541,274. , Ibid 2,54
1, 230, Japanese Patent Publication No. 53-41091, European Patent Publication No. 029104, and the like, and a dispersion method using an organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723.

As the high-boiling-point organic solvent that can be used in the above-mentioned oil-in-water dispersion method, phthalic acid esters (for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2 , 4-di-ter
t-amylphenyl) isophthalate, bis (1,1-
Diethylpropyl) phthalate), esters of phosphoric acid or phosphones (eg, diphenylphosphate, triphenylphosphate, tricresylphosphate, 2
-Ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexyl phenyl phosphate), benzoic acid esters (for example, 2-ethylhexyl benzoate, 2,4-dichloro) Benzoate, dodecylbenzoate, 2-ethylhexyl-p-
Hydroxybenzoate), amides (eg N, N
-Diethyldodecane amide, N, N-diethyllaurylamide), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic esters (eg, dibutoxyethyl succinate, Di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate,
Trioctyl citrate), aniline derivative (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline, etc., chlorinated paraffins (chlorine content 10% to
80% paraffins) trimesic acid esters (eg tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (eg 2,
4-di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4- (4-dodecyloxyphenylsulfonyl)
Phenol), carboxylic acids (for example, 2- (2,4-
Di-tert-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkylphosphoric acids (for example, di-2
(Ethylhexyl) phosphoric acid, diphenyl phosphoric acid) and the like. As an auxiliary solvent, it has a boiling point of 30 ° C or higher and about 1
An organic solvent at 60 ° C. or lower (for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide) may be used in combination. The high boiling point organic solvent is used in an amount of 0 to 2.0 times the weight of the coupler, preferably 0.
It can be used in an amount up to 1.0 times.

The present invention can be applied to any light-sensitive material, and various additives other than the compounds represented by the general formula (I) or (II) can be added to the photographic constituent layers. For details, see the following patent publications, especially European patent EP0,
Those described in 355,660A2 (Japanese Patent Application No. 1-107011) are preferably used.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

As other cyan couplers, in addition to the diphenylimidazole type cyan couplers described in JP-A-2-33144, European Patent EP 0,333,1
No. 85A2, 3-hydroxypyridine cyan couplers (among others, couplers listed as specific examples (4
(Especially preferred are couplers (6) and (9), which are obtained by adding a chlorine-leaving group to the 4-equivalent coupler of 2) to make them 2-equivalent).
Alternatively, the cyclic active methylene cyan couplers described in JP-A No. 64-32260 (coupler examples 3, 8, and 34 listed as specific examples are particularly preferable) may be used in combination.

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide and the like can be used, but the above-mentioned objects are particularly effective. In order to achieve this, it is preferable to use a silver chlorobromide or silver chloride emulsion having a silver chloride content of substantially 90 mol% or more, further 95% or more, and particularly 98% or more, which is substantially free of silver iodide. Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer is added to the European Patent E for the purpose of improving image sharpness and the like.
P0,337,490A2, pages 27 to 76, dyes that can be decolorized by processing (among others, oxonol dyes) are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more. It is preferable that the water-resistant resin layer of the support contains 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a divalent to tetravalent alcohol (eg, trimethylolethane). ..

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler. That is, the compound (F) that chemically bonds with the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the aroma remaining after the color development processing. The use of the compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine color developing agent, simultaneously or solely, for example, in storage after processing. It is preferable in order to prevent stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or its oxidant.

In order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material according to the present invention has an anti-mold property as described in JP-A-63-271247. It is preferable to add an agent. The support used in the light-sensitive material according to the present invention may be a white polyester-based support for a display or a support provided with a layer containing a white pigment on the support having a silver halide emulsion layer. You may use. Further, in order to improve the sharpness, it is preferable to coat an antihalation layer on the side of the support coated with the silver halide emulsion layer or on the back surface. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low illuminance exposure or high illuminance short time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, upon exposure, it is preferable to use the band stop filter described in U.S. Pat. No. 4,880,726. As a result, the light color mixture is removed, and the color reproducibility is significantly improved. Hereinafter, the processing of the present invention will be described in detail. In the present invention,
The photographic light-sensitive material is color-developed, desilvered, and washed (or stabilized) with water.

In the color developer used in the present invention,
It contains a known aromatic primary amine color developing agent.
A preferable example is a p-phenylenediamine derivative, and as a representative example, N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-
Amino-5- (N-ethyl-N-laurylamino) toluene, 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (β -Hydroxyethyl) amino] aniline, 4
-Amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -aniline, N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide, N, N-dimethyl-p -Phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline, 4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-butoxyethylaniline and the like can be mentioned. Particularly preferred is 4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -aniline. Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is the amount of developer 1
The concentration is preferably about 0.1 g to about 20 g, and more preferably about 0.5 g to about 10 g per liter.

In carrying out the present invention, in the work environment,
It is preferred to use a developer which is substantially free of benzyl alcohol. Here, “not substantially containing” means
The concentration of benzyl alcohol is preferably 2 ml / liter or less, more preferably 0.5 ml / liter or less, and most preferably benzyl alcohol is not contained at all. The color developing solution used in the present invention should contain substantially no sulfite ion (substantially no sulfite ion concentration of 3.0) in order to suppress variations in photographic characteristics due to continuous processing. X10 ^-3 mol / liter or less) is more preferable. Most preferably, it contains no sulfite ion at all. Here, however, in the present invention, a very small amount of sulfite ion used for the antioxidant of the processing agent kit in which the developing agent is concentrated before preparing the use solution is excluded.

The color developing solution used in the present invention preferably contains substantially no sulfite ion, but in order to suppress the fluctuation of photographic characteristics due to the fluctuation of the concentration of hydroxylamine, it further contains hydroxylamine. It is more preferable not to do this (the term "substantially free from" means a hydroxylamine concentration of 5.0 x 10 ^-3 mol / liter or less). Most preferably, it contains no hydroxylamine at all.

The color developing solution used in the present invention more preferably contains an organic preservative in place of the hydroxylamine and sulfite ion. Here, the organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being added to the processing solution of the color photographic light-sensitive material. That is, it is an organic compound having a function of preventing oxidation of a color developing agent due to air, etc. Among them, hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyl Particularly effective organic compounds include ketones, α-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed amines. It is a preservative. These are disclosed in JP-B-48-30496, JP-A-52-143020, JP-A-63-1235, and JP-A-63-1235.
No. 30845, No. 63-21647, No. 63-446
55, 63-53551, 63-43140.
No. 63, No. 63-56654, No. 63-58346, No. 63-43138, No. 63-146041, No. 63.
-44657, 63-46656, U.S. Pat. Nos. 3,615,503, 2,494,903, JP-A-1-97953, 1-186939, 1-1.
86940, 1-187557, 2-3062.
No. 44 and the like. Other preservatives include various metals described in JP-A-57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, JP-A-63-239447 and JP-A-63.
-128340, JP-A-1-186939 and 1-
Amines such as those described in 187557, JP-A-5
Alkanolamines described in JP-A-4-3532, JP-A-SHO-5
Polyethyleneimines described in 6-94349, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be used as necessary. In particular, alkanolamines such as triethanolamine, N, N-
Dialkylhydroxylamine such as diethylhydroxylamine and N, N-di (sulfoethyl) hydroxylamine, hydrazine derivative (excluding hydrazine) such as N, N-bis (carboxymethyl) hydrazine, and catechol-3,5-disulfone. The addition of aromatic polyhydroxy compounds represented by acid soda is preferred.

In particular, the combined use of the dialkylhydroxylamine and / or hydrazine derivative and the alkanolamines improves the stability of the color developer,
Therefore, it is more preferable from the viewpoint of improving stability during continuous treatment.
In the present invention, chlorine ions are contained in an amount of 0.08 mol / liter or more for the purpose of suppressing fog and improving processing dependence. It preferably contains 0.09 to 0.5 mol / liter. Below this concentration, fog is likely to occur and the processing dependency is not improved. If the concentration is too high,
A decrease in maximum concentration occurs.

In the present invention, bromine ions are contained in the color developing solution in an amount of 3.0 × 10 ^-5 mol / liter to 1.0 × 10 ^-3.
It is preferable to contain it in mol / liter. More preferably, it is 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol / liter. When the bromine ion concentration is more than 1 × 10 ^-3 mol / liter, the development is delayed, the maximum density and the sensitivity are lowered,
If it is less than 3.0 × 10 ⁻⁵ mol / liter, fog cannot be sufficiently prevented. Here, chlorine ion and bromine ion may be directly added to the developing solution, or may be eluted from the light-sensitive material to the developing solution during the development processing. When added directly to the color developer, examples of the chlorine ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, magnesium chloride and calcium chloride. Further, it may be supplied from a fluorescent whitening agent added to the color developing solution.

Examples of the bromine ion supplying substance include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide and magnesium bromide.
When it is eluted from the light-sensitive material during the development processing, both chlorine ions and bromine ions may be supplied from the emulsion or may be supplied from sources other than the emulsion. The color developer used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 1.
It is 1.0, and the color developing solution can contain other compounds of known developing solution components. Above pH
It is preferable to use various buffering agents in order to retain the. As the buffering agent, 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 salt, trishydroxyaminomethane salt, lysine salt, etc. Can be used. Particularly, carbonate, phosphate, tetraborate, and hydroxybenzoate have excellent solubility and buffering ability in a high pH region of pH 9.0 or more, and even if added to a color developing solution, they adversely affect photographic performance. It is particularly preferable to use these buffers, because they have the advantages of being free from (fogging, etc.) and being inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
2-hydroxybenzoic acid potassium (potassium 5-sulfosalicylate) etc. can be mentioned. The amount of the buffer added to the color developing solution is preferably 0.1 mol / liter or more, and particularly 0.1 mol / liter to 0.1.
It is particularly preferably 4 mol / liter. In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for 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'-tetramethylene sulfonic acid, trans-cyclohexanediaminetetraacetic acid,
1,2-diaminopropane tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N ' Examples include -bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid and hydroxyethyliminodiacetic acid. Two or more of these chelating agents may be used in combination, if necessary. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. For example, 0.1 per liter
It is about g to 10 g.

Any development accelerator can be added to the color developing solution if necessary. As a development accelerator, Japanese Patent Publication No. Sho 37
-16088, 37-5987, 38-782.
No. 6, No. 44-12380, No. 45-9019 and the thioether compounds represented by US Pat. No. 3,813,247, and JP-A Nos. 52-49829 and 50-49.
P-phenylenediamine compounds represented by JP-A-15554, JP-A-50-137726, and JP-B-44-3.
0074, JP-A-56-156826 and 52-
Quaternary ammonium salts represented by U.S. Pat. No. 4,434,329, U.S. Pat. Nos. 2,494,903 and 3,128,182.
Nos. 4,230,796, 3,253,919
No. 4, Japanese Patent Publication No. 41-11431, U.S. Pat. No. 2,48
2,546, 2,596,926 and 3,58
Amine compounds described in 2,346, etc., JP-B-37-
16088, 42-25201, U.S. Pat.
128,183, Japanese Patent Publication Nos. 41-11431, 42
-23883 and U.S. Pat. No. 3,532,501, and other polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary. The benzyl alcohol is as described above.

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

Color developing solutions applicable to the present invention include:
It preferably contains an optical brightener. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 to 5 g / liter, preferably 0.1 g to 4 g / liter. If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid, polyalkyleneimine and the like may be added. The treatment temperature applied to the present invention is 36 ° C or higher, preferably 37 ° C to 4 ° C.
It is 5 ° C. Below this temperature, a sufficient color density cannot be obtained, and the processing dependence deteriorates. The processing time of the present invention is 50 seconds or less, preferably 10 to 45 seconds. If it is longer than the main processing time, fogging tends to occur, which is not preferable. It is preferable that the replenishment amount is small, but the photosensitive material is 1 m.
^{20 to} 600 ml per ² is suitable, and preferably 3
0 ml to 200 ml, more preferably 40 ml to 15
It is 0 ml.

The photographic emulsion layer after color development is desilvered. In the desilvering process, the bleaching process and the fixing process may be performed separately or may be performed simultaneously (bleach-fixing process). Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment may be optionally carried out. In particular, the present invention is particularly effective when a bleach-fixing solution is used immediately after color development. That is, when the bleach-fixing solution is mixed in the color developing solution in the pre-bath during various troubles, the color developing tank solution needs to be replaced because it significantly affects the photographic characteristics. However, under the present invention, the effect of mixing is remarkably reduced, and it becomes possible to maintain photographic characteristics to some extent. In particular, the amount of the bleach-fixing solution mixed is effective in the range of 0.1 to 5 ml, preferably 0.2 to 2 ml, per liter of color development.

Examples of the bleaching agent used in the bleaching solution and the bleach-fixing solution include iron salts; compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II); peracids. Quinones; nitro compounds and the like. Typical bleaching agents are iron chloride; ferricyanide; dichromate; iron
Organic complex salts of (III) (for example, metal complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid) ); Persulfate; Bromate; Permanganate; Nitrobenzenes and the like. Of these, ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropaneirontetraacetic acid iron
(III) Iron (III) aminopolycarboxylates including complex salts
Complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The bleaching solution or bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is used at a pH of 3.0 to 8.

Known additives such as rehalogenating agents such as ammonium bromide and ammonium chloride; pH buffering agents such as ammonium nitrate; metal corrosion inhibitors such as ammonium sulfate are added to the bleaching solution and the bleach-fixing solution. be able to. In the bleaching solution and bleach-fixing solution, in addition to the above compounds,
An organic acid is preferably contained for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (pk
a) is a compound of 2 to 5.5, and specifically, acetic acid, propionic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Is most commonly used, with ammonium thiosulfate being the most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, in the fixing solution and the bleach-fixing solution, various aminopolycarboxylic acids and organic phosphonic acids (for example, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N ′, N ′) are used for the purpose of stabilizing the solution. -Ethylenediaminetetraphosphonic acid) is preferred.

The fixing solution and the bleach-fixing solution may further contain various fluorescent whitening agents, defoaming agents, surfactants, polyvinylpyrrolidone, methanol and the like. Bleach,
If necessary, a bleaching accelerator can be used in the bleach-fixing solution and the prebath thereof. Specific examples of useful bleaching accelerators include U.S. Pat. No. 3,893,858, West German Patents 1,290,812 and 2,059,988,
JP-A Nos. 53-32736, 53-57831, 53-37418, 53-72623, 53-
No. 95630, No. 53-95631, No. 53-104
No. 232, No. 53-124424, No. 53-1416
No. 23, No. 53-28426, Research Disclosure No. 17129 (July 1978) and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A No. 50-140129; 45-8506, JP-A-52-208
32, No. 53-32735, U.S. Pat. No. 3,70.
Thiourea derivatives described in 6,561; West German Patent No. 1,
127,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,74.
No. 8,430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-42434, 49-59644, 53-94927, 54-35727. , 55-
26506 and 58-163940;
Bromide ion etc. can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat. No. 3,893,858.
, West German Patent No. 1,290,812, JP-A-53-9
The compounds described in 5630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable.
These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

The total time for the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 10 seconds
It is 3 minutes, more preferably 20 seconds to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. Specific methods for strengthening stirring are disclosed in JP-A-62-183460 and 62-183.
No. 461, a method of causing a jet of a processing solution to collide with the emulsion surface of the light-sensitive material, a method of improving the stirring effect by using a rotating means of JP-A-62-183461, and a wiper blade provided in the solution. And the emulsion surface are brought into contact with each other to make the emulsion surface turbulent, thereby further improving the stirring effect, and increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The color light-sensitive material of the present invention generally undergoes a washing step after desilvering. A stable process may be performed instead of the water washing process. In such stabilization treatment, JP-A-57-8543, JP-A-58-14834,
All the known methods described in JP-A-60-220345 can be used. Further, a water washing step-stabilization step may be carried out in which a stabilizing bath containing a dye stabilizer and a surfactant, which is represented by processing of a color light-sensitive material for photographing, is used as a final bath. The washing solution and stabilizing solution include inorganic phosphoric acid,
Water softeners such as polyaminocargonic acid and organic aminophosphonic acids; metal salts such as Mg salt, Al salt, Bi salt;
A surfactant; a hardener and the like can be contained.

The amount of washing water in the washing step depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), the purpose of use, the washing water temperature, the number of washing tanks (number of stages), replenishment methods such as countercurrent and forward flow, and other various It can be set in a wide range depending on the condition. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Pictu.
re and Television Engineers Volume 64, p. 248 ~
253 (May 1955 issue). Further, as a solution to problems such as bacterial growth and adherence of generated floating substances to a light-sensitive material which occur when the amount of washing water is greatly reduced in a multi-stage countercurrent system, it is described in JP-A-62-288838. Calcium ion,
The method of reducing magnesium ions can be used very effectively. Also, isothiazolone compounds, siabendazoles, chlorine-based bactericides such as chlorinated sodium isocyanurate described in JP-A-57-8542, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Hygiene Engineering Society, "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used.

The washing water has a pH of 4-9, preferably 5-8. The washing water temperature and washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc.
20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds
A range of 5 minutes is selected. Examples of dye stabilizers that can be used in the stabilizing solution include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. In addition, the stabilizing solution contains other pH adjusting buffers such as boric acid and sodium hydroxide;
1-Hydroxyethylidene-1,1-diphosphonic acid; a chelating agent such as ethylenediaminetetraacetic acid; an antisulfurizing agent such as an alkanolamine; an optical brightening agent; a mildewproofing agent and the like can be contained. The overflow solution that accompanies the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration.

A color developing agent may be incorporated in the color light-sensitive material of the present invention for the purpose of simplifying and accelerating the processing, and it is preferable to use various precursors of the color developing agent for incorporation. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, and No. 3,342,59.
No. 9, RD magazines No. 14850 and No. 15159, Schiff base type compounds, No. 13924 aldol compounds, U.S. Pat. No. 3,719,492, metal salt complexes, JP Urethane compounds described in JP-A-53-135628 can be mentioned. The color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. A typical compound is JP-A-56-64339.
No. 57-144547 and No. 58-11543.
No. 8 etc.

The coupler of the present invention can be applied to, for example, a color paper, a color reversal paper, a direct positive color light-sensitive material, a color negative film, a color positive film, a color reversal film and the like. Of these, application to a color light-sensitive material having a reflective support (for example, color paper, color reversal paper) is preferable, and application to a color light-sensitive material having a reflective support is particularly preferable.

[0100]

According to the method of the present invention, photographic fluctuations are small and sufficient color developability can be obtained even with rapid processing. Further, by using the cyan coupler of the present invention and defining the chlorine ion concentration in the color developing solution, cyan fog can be remarkably suppressed even if the bleach-fix solution is mixed (contaminated) with the color developing solution.

[0101]

【Example】

Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated to form a layer structure shown below. A multilayer color printing paper (101) was prepared. The coating liquid was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-3) 16.0 g, solvent (Solv-1) 25 g, solvent (Solv-2) 25
g and 180 cc of ethyl acetate and dissolved in 10%
An emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of a 10% gelatin aqueous solution containing 60 cc of sodium dodecylbenzenesulfonate and 10 g of citric acid. On the other hand, a silver chlorobromide emulsion A (a cube, a 3: 7 mixture of a large size emulsion A having an average grain size of 0.88 μm and a small size emulsion A having a grain size of 0.70 μm (silver molar ratio). The variation coefficient of the grain size distribution is , 0.08 and 0.10 respectively, and silver bromide 0.
3 mol% localized on a part of the particle surface) was prepared.
In this emulsion, blue-sensitive sensitizing dyes A and B shown below were added to the large-sized emulsion A per mol of silver to 2.0 × each.
10 ⁻⁴ , and for small size emulsion A, 2.
5 × 10 ⁻⁴ mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A are mixed and dissolved,
The first layer coating solution was prepared so as to have the composition shown below.

Preparation of coating solution for the fifth layer Cyan coupler (ExC) 33.0 g, ultraviolet absorber (UV-2) 18.0 g, color image stabilizer (Cpd-1) 3
0.0 g, color image stabilizer (Cpd-9) 15.0 g, color image stabilizer (Cpd-10) 15.0 g, color image stabilizer (Cp
d-11) 1.0 g, color image stabilizer (Cpd-8) 1.0
g, color image stabilizer (Cpd-6) 1.0 g, solvent (Sol
v-6) 22.0 g and solvent (Solv-1) 1.0 g were dissolved by adding 60.0 cc of ethyl acetate, and this solution was added to 500 cc of 20% gelatin aqueous solution containing 8 cc of sodium dodecylbenzenesulfonate. An ultrasonic dispersion was prepared by emulsifying and dispersing with an ultrasonic homogenizer. on the other hand,
Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C having a grain size of 0.41 μm (Ag molar ratio). The coefficient of variation of grain size distribution is 0. 09 and 0.11, A for each size emulsion
0.8 mol% of gBr was locally contained in a part of the particle surface) was adjusted. In this emulsion, the red sensitizing dye E shown below was added to a large size emulsion in an amount of 0.9 per mole of silver.
× 10 ^-4 mol, or 1.1 × 1 for small emulsions
^0-4 mol is added. Further, compound F shown below was added in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution for the fifth layer having the composition shown below.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Cpd-14 and C are added to each layer.
The total amount of pd-15 is 25.0 mg / m ² and 50 mg / m ² , respectively.
It was added so as to be m ² . The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0105]

[Table 6]

[0106]

[Table 7]

[0107]

[Table 8]

Further, 1- (5-methylureidophenyl) is added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
-5-Mercaptotetrazole was added in an amount of 8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol and 2.5 x 10 ^-4 mol per mol of silver halide, respectively. Further, 4-hydroxy-6-methyl- was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
1,3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. To prevent irradiation, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer.

[0109]

[Chemical 27]

(Layer Constitution) The composition of each layer is shown below. Numbers represent coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

[0111]

[Table 9]

[0112]

[Table 10]

[0113]

[Table 11]

[0114]

[Table 12]

[0115]

[Chemical 28]

[0116]

[Chemical 29]

[0117]

[Chemical 30]

[0118]

[Chemical 31]

[0119]

[Chemical 32]

[0120]

[Chemical 33]

[0121]

[Chemical 34]

[0122]

[Chemical 35]

Next, samples 102 to 109 were prepared by changing the cyan coupler of sample 101 as follows. Sample 102 Cyan coupler A

[0124]

[Chemical 36]

Sample 103 Cyan coupler B

[0126]

[Chemical 37]

Sample 104 Cyan coupler C

[0128]

[Chemical 38]

Sample 105 Cyan coupler D (compound described in EP 0249453)

[0130]

[Chemical Formula 39]

Sample 106 Cyan coupler of the present invention (1) Sample 107 Cyan coupler of the present invention (3) Sample 108 Cyan coupler of the present invention (18) Sample 109 Cyan coupler of the present invention (39) Obtained as described above Photographic papers 101-109 were exposed to 250 CMS through a wedge wedge and processed in the following processing steps. Processing step Temperature time (second) Color development 39 ° C. 45 Bleach fixing 30-35 ° C. 45 Rinse 30-35 ° C. 20 Rinse 30-35 ° C. 20 Rinse 30-35 ° C. 20 Rinse 30-35 ° C. 30 Composition of each processing solution is It is as follows.

[Color developer] Tank liquid water 800 ml EDTA.2Na 3 g catechol-3,5-sodium disulfonate 0.3 g triethanolamine 8.0 g potassium bromide 0.03 g sodium chloride See Table 13 N, N-di (Sulfoethyl) hydroxylamine 5.0 g Optical brightener (WHITEX 4, manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g Sodium triisopropylnaphthalene-β-sulfonate 0.3 g N-ethyl-N- (β-methanesulfonamidoethyl)- 3-Methyl-4-aminoaniline sulfate 5.0 g Water was added to 1000 ml pH (25 ° C) 10.05

Bleach-fixing tank liquid Water 800 ml Ammonium thiosulfate (50% by weight) 120 ml Ammonium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 60 g Ethylenediaminetetraacetic acid / 2Na 3 g Glacial acetic acid 7 g Water 1000 ml pH (25 ° C.) 5. 50 Rinse solution Ion-exchanged water (calcium and magnesium are each 3 ppm or less) The sodium chloride concentration of the color developing solution was changed as shown in Table 13, and the pH was further adjusted from 10.05 to ± 0.
Table 13 shows the amount of change in the concentration from the standard pH at the exposure amount that gives a concentration of 0.8 at the standard pH of cyan at each sodium chloride concentration of 15 changes.

[0134]

[Table 13]

With the chloride ion concentration of the present invention, when the cyan coupler of the present invention was used, the decrease in the sensitivity when the pH was lowered was small, and the increase in the sensitivity when the pH was raised was also small, and the processing dependence was remarkably improved.

Example 2 Similar to the process of Example 1, except that the bleach-fix solution was added to the color developing solution in an amount of 0.1 ml / liter, and the cyan unexposed areas of each of the samples 101 to 109 before and after addition ( Table 14 shows the change in the concentration of Dmin).

[0137]

[Table 14]

In Table 14, the samples of the present invention (106-
When 109) was treated with the chlorine ion concentration of the present invention, the increase of Dmin was small even when the bleach-fixing solution was mixed, and good photographic characteristics were obtained.

Example 3 The surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated to prepare the following. A multilayer color photographic printing paper 301 having the layer structure shown was produced. The coating liquid was prepared as follows.

Preparation of coating solution for fifth layer Cyan coupler (ExC) 32.0 g, color image stabilizer (C
pd-2) 3.0 g, color image stabilizer (Cpd-4) 2.0
g, color image stabilizer (Cpd-6) 18.0 g, color image stabilizer (Cpd-7) 40.0 g and color image stabilizer (Cpd-).
8) 5.0 g, ethyl acetate 50.0 cc and solvent (S
olv-6) 14.0 g was added and dissolved, and this solution was added with 20% sodium dodecylbenzenesulfonate 8 cc.
After adding to 500 cc of gelatin aqueous solution, it was emulsified and dispersed by an ultrasonic homogenizer to prepare an emulsified dispersion.
On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.58
A 1: 4 mixture of a large size emulsion (μm) and a small size emulsion (0.45 μm) (Ag molar ratio). Coefficients of variation of grain size distribution are 0.09 and 0.11, respectively.
0.6 mol% of gBr was locally contained in a part of the particle surface) was prepared. In this emulsion, the red sensitizing dye E shown below was added to a large size emulsion in an amount of 0.9 per mole of silver.
× 10 ^-4 mol, or 1.1 × 1 for small emulsions
^0-4 mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution for the fifth layer having the composition shown below.

Coating solutions for the first to fourth layers, the sixth layer and the seventh layer were prepared in the same manner as the fifth layer coating solution. As a gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Further, the total amount of Cpd-10 and Cpd-11 in each layer was 25.
It was added to a 0 mg / m ² and 50.0 mg / m ^2. The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer.

Sensitizing dye A

[0143]

[Chemical 40]

And sensitizing dye B

[0145]

[Chemical 41]

(2.0 × 10 ^-4 mol for large size emulsion and 2.5 × 10 ^-4 mol for small size emulsion per mol of silver halide) [Green-sensitive emulsion] Layer] Sensitizing dye C

[0147]

[Chemical 42]

(Per mol of silver halide, 4.0 × 10 ^-4 mol for large size emulsion, 5.6 × 10 ^-4 mol for small size emulsion) and sensitizing dye D

[0149]

[Chemical 43]

(7.0 × 10 ⁻⁵ mol for large size emulsion and 1.0 × 10 ⁻⁵ mol for small size emulsion per mol of silver halide) [Red-sensitive emulsion layer] Sensitizing dye E

[0151]

[Chemical 44]

(0.9 × 10 ⁻⁴ mol for large size emulsion and 1.1 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) Further, the following compounds were halogenated. 2.6 × per mol of silver halide
10 ⁻³ mol was added.

[0153]

[Chemical 45]

1- (5-methylureidophenyl) is added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
-5-Mercaptotetrazole was added in an amount of 8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol and 2.5 x 10 ^-4 mol per mol of silver halide, respectively. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ⁻⁴ mol and 2 mol, respectively, per mol of silver halide. × 10 ⁻⁴ mol was added. Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer in order to prevent irradiation.

[0155]

[Chemical 46]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average grain size 0 3: 8 mixture of large size emulsion of 0.88μ and small size of 0.70μ (silver molar ratio), variation coefficient of grain size distribution is 0.08 and 0.10 respectively, and silver bromide for each size emulsion 0.30% by mole localized on a part of the particle surface) 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0 .18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0.06

Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitivity) Emulsion layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion having an average grain size of 0.55μ and small size emulsion of 0.39μ (Ag molar ratio). The coefficient of variation of grain size distribution is respectively 0.10 and 0.08, 0.8 mol% of AgBr was locally contained in a part of the grain surface in each size emulsion) 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40

Fourth Layer (UV Absorbing Layer) Gelatin 1.58 UV Absorbing Agent (UV-1) 0.47 Color Mixing Inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth Layer ( Red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion with average grain size 0.58μ and small size emulsion with 0.45μ (Ag mole ratio). Coefficient of variation of grain size distribution Is 0.09 and 0.11, and AgBr 0.6 mol% is locally contained in a part of the grain surface in each size emulsion) 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stability Agent (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer ( Cpd-8) 0.05 Solvent (Solv-6) 0.14

Sixth Layer (UV Absorbing Layer) Gelatin 0.53 UV Absorbing Agent (UV-1) 0.16 Color Mixing Preventing Agent (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh Layer ( Protective layer) Gelatin 1.33 Polyvinyl alcohol acrylic modified copolymer (Degree of modification 17%) 0.17 Liquid paraffin 0.03

[0160]

[Chemical 47]

[0161]

[Chemical 48]

[0162]

[Chemical 49]

[0163]

[Chemical 50]

[0164]

[Chemical 51]

[0165]

[Chemical 52]

[0166]

[Chemical 53]

[0167]

[Chemical 54]

[0168]

[Chemical 55]

The cyan coupler of the sample 301 thus obtained was replaced by the following cyan coupler of equimolar amount.
305 was created. Sample 302 Same as Example 1, Cyan Coupler A. Sample 303 Cyan coupler E (JP-A-64-5)
52 exemplified compounds)

[0170]

[Chemical 56]

Sample 304 Cyan Coupler (1) of the Present Invention (Sample) 305 Thin Coupler (3) of the Present Invention The above samples 301 to 305 were exposed to 250 CMS through a wedge wedge and processed in the following processing steps. However, the processing time of the color developer is 30 seconds and 60 seconds,
The treatment temperature was 35 ° C and 38 ° C. The chlorine ion concentration of the color developing solution was changed as shown in Table 15.

Processing Step Temperature Time (sec) Color Development 35 ° C., 38 ° C. See Table Bleach Fixing 30-35 ° C. 45 Rinse 30-35 ° C. 20 Rinse 30-35 ° C. 20 Rinse 30-35 ° C. 20 Rinse 30-35 ° C. 30 The composition of each treatment liquid is as follows.

[Color developer] Tank liquid water 800 ml Diethylenetriaminepentaacetic acid 3 g Sodium catechol-3,5-disulfonate 0.3 g Triethanolamine 8.0 g Potassium bromide 0.03 g Sodium chloride See Table 15 Diethylhydroxylamine 5. 0 g Optical brightener (WHITEX 4, manufactured by Sumitomo Chemical) 1.0 g Sodium triisopropylnaphthalene-β-sulfonate 0.3 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino Aniline sulphate 4.0g Water added 1000ml pH (25 ° C) 10.05

The same bleach-fixing solution and rinsing solution as in Example 1 were used. Under each processing condition, the change in density at the sensitivity point when the density of the color developing agent was changed by ± 1.5 g was determined in the same manner as in Example 1. The results are shown in Table 15.

[0175]

[Table 15]

Photosensitive materials of the present invention (Samples 304 and 305)
Was processed under the conditions of color development of the present invention, stable photographic characteristics could be obtained with almost no change in sensitivity even if the concentration of the main agent was changed.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 8, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0088

[Correction method] Change

[Correction content]

Examples of the bleaching agent used in the bleaching solution and the bleach-fixing solution include iron salts; compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II); peracids. Quinones; nitro compounds and the like. Typical bleaching agents are iron chloride; ferricyanide; dichromate; iron
(III) Organic complex salts (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, nitrilodiacetic acid monopropionic acid, ethylenediamine N, Examples thereof include metal complex salts such as aminopolycarboxylic acids such as N-disuccinic acid and propylenediamine N, N'-disuccinic acid); persulfates; bromates; permanganates; nitrobenzenes. Of these, aminopolycarboxylic acid irons such as ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts
(III) Complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The bleaching solution or bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is used at a pH of 3.0 to 8.

Claims (2)

[Claims] 1. A method of color developing and desilvering an exposed halogenated color photographic light-sensitive material, wherein the red-sensitive emulsion layer constituting the light-sensitive material is represented by the following general formula (I) or (II). A method for processing a silver halide color photographic light-sensitive material, which comprises using a color developing solution containing at least one pyrrolotriazole type cyan coupler and performing the color development with a chlorine ion content of 0.08 mol / liter or more. [Chemical 1] (In formula, Za and Zb are -C (R < ₃ >) = or -N, respectively.
Represents =. However, one of Za and Zb is -N =
, And the other is -C (R ₃₎ is =. R ₁ and R ₂ each represent an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more, and the sum of 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 splitting off in a coupling reaction with an oxidation product of an aromatic primary amine color developing agent. The group of R ₁ , R ₂ , R ₃ or X may be a divalent group and may be bonded to a dimer or higher polymer or a polymer chain to form a homopolymer or a copolymer. ) 2. A silver halide color photographic light-sensitive material comprising at least one high silver chloride emulsion containing 90 mol% or more of chlorine ions.
The silver halide color photographic light-sensitive material processing method according to claim 1, wherein the silver halide color photographic light-sensitive material is contained in a layer.