JPH05204110A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color development performance and to enhance fastness and color reproducibility of a color image by forming a layer containing the combination of a specified pyrrolotriazole type cyan coupler and a specified phenol or naphthol type cyan coupler. CONSTITUTION:A silver halide emulsion layer contains at least each one kind of the pyrrolotriazole type cyan coupler represented by formula I or II and the phenol or naphthol type cyan coupler represented by formula III. In formulae I-III, 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 R1 and R2 of >=0.65; R3 is H or a substituent; X is H or a group to be released by coupling with the oxidation product of an aromatic primary amine color developing agent; R11 is alkyl, aryl, etc., R12 is >=2C alkyl; R13 is H, alkyl, or the like; X' is same as X; and n is 0 or 1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material having improved color image fastness and color reproducibility by using a novel pyrrolotriazole cyan coupler in combination with other cyan couplers.

[0002]

BACKGROUND OF THE INVENTION Phenolic and naphthol couplers are well known as cyan couplers generally used in silver halide color photographic light-sensitive materials.
On the other hand, in recent years, the color development (coupling activity and spectral absorption coefficient of the obtained dye) of these phenol-based and naphthol-based couplers, the fastness of the obtained color image, the absorption characteristics of the color image, etc. have been improved and The development of couplers that provide color developability, color image fastness, and excellent color reproducibility has been advanced and proposed as new cyan couplers. For example, 3-hydroxypyridine compounds described in European Patent No. 333,185, 3H-2-dicyanomethylidene thiazoles described in European Patent No. 362,808, and JP-A No. 64-32260. 3-dicyanomethylidene-2,3-dihydrobenzothiophene-1,1-dioxides, pyrazoloazoles described in JP-A-63-264753 and US Pat. No. 4,873,183, and US Pat. 4,818,672, 4,921,783
And imidazoles described in JP-A-3-48243, European Patent Publication Nos. 304,001 and 329,
036, 374, 781 and JP-A-2-858.
Examples thereof include pyrazolopyrimidones and pyrazoloquinazolones described in JP-A-51, and condensed ring triazoles described in EP-A-342,637.

However, the performance of these proposed new cyan couplers cannot satisfy the above-mentioned color development, color image fastness, color reproducibility, etc. at the same time, and cannot be put to practical use unless further research is conducted. The current situation.
It was also found that the mutual use of these couplers or the combined use of the above-mentioned phenol-based and naphthol-based cyan couplers do not complement each other's excellent performances, but rather tend to deteriorate.

The pyrrolotriazole type cyan couplers according to the present invention and the couplers having the same mother structure as the couplers of the general formulas (II) to (XXXV) in the examples of JP-A-62-278552 are represented by the general formulas (IX) and (XIII). ), (XV) and (XXII), each showing two specific compounds. Further, the general formulas (I) and (II) of JP-A-62-279340 show the same mother nucleus structure, and 42 kinds of specific compounds are exemplified. However, this JP-A-62-27855
No. 2 and No. 62-279340 are magenta couplers, which are dyes obtained by a coupling reaction with an oxidant of a color developing agent by a substituent introduced even though they have the same mother nucleus structure. Which is a cyan dye is completely different from the cyan coupler of the present invention.
Further, JP-A-1-288855 presents general formulas (IV) to (XVII) as cyan couplers having a new mother nucleus, among which general formulas (IV) and (V) are described as pyrrolotriazole cyan couplers. Has been done. In particular, the general formula (IV) is a pyrrolotriazole-based coupler having the same mother nucleus structure, but the structure shown in the patent has the active site for coupling reaction with the oxidant of the color developing agent as the coupler of the present invention. Are different from each other, and the coupling activity of the couplers exemplified in the patent is low and it is difficult to put them into practical use.

[0005]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above,
Conventional phenol-based and naphthol-based cyan couplers and the above-mentioned new cyan couplers such as hydroxypyrimidines all satisfy color development, color image storability / fastness, and color reproducibility at the same time even when used alone or in combination. It does not show performance, but rather deteriorates and deteriorates individual excellent performance when used in combination. Therefore, there is a demand for a novel combination of cyan couplers, which retains the excellent performance of each coupler even when used in combination with a conventional cyan coupler and complements the disadvantages of each coupler and shows better performance. Therefore, the first object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in color image storability and fastness. The second purpose is to provide a silver halide color photographic light-sensitive material which provides high color development. The third object is to provide a silver halide color photographic light-sensitive material excellent in color reproducibility.

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies to achieve the above-mentioned objects, and as a result, they have been able to achieve the objects by the means described below. That is, in a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, a pyrrolotriazole type cyan coupler represented by the following general formula (I) or (II) is contained in the silver halide emulsion layer. At least one of the following general formula (II
A silver halide color photographic light-sensitive material containing at least one selected from cyan couplers represented by I), (IV), (V) or (VI).

[0007]

[Chemical 3]

(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. )

[0009]

[Chemical 4]

In the general formulas (III) and (IV), R ₁₁
Represents an alkyl group, an aryl group or a heterocyclic group, and R
₁₂ represents an alkyl group having 2 or more carbon atoms, R ₁₃ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carbonamido group or a ureido group, and R ₁₄ represents an alkyl group, an aryl group. Represents a group, a heterocyclic group, an alkoxy group, an aryloxy group, or an amino group, and 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, n represents 0 or 1. R ₁₂ and R ₁₃ of the general formula (III) may be bonded to each other to form a ring, and R ₁₃ and R ₁₄ of the general formula (IV) may be bonded to each other to form a ring. In the formula, R ¹ is a hydrogen atom, an alkyl group,
An alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an amino group or an aryl group; R ² represents a group capable of substituting for a benzene ring;
³ and R ⁴ represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group or an aryloxy group, R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group or an aryl group, and t is an integer of 0 to 4 And m is 0-4
Represents the integer.

The present invention will be described in detail below. First, general formulas (I) and (II) will be described.

Za and Zb each represent --C (R ₃ ) = or --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).

[0013]

[Chemical 5]

(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, 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, 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, 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 preferably, it is an alkyl group or an aryl group having at least one alkoxy group, 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 (Mc Gr
aw-Hill) and "Special Issue on Chemistry", No. 122, 96-1
Details on page 03, 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 .

[0022] 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 aryloxycarbonyl group, 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 preferable R ₂ is an aryloxycarbonyl group or an alkoxycarbonyl group, and the most preferable 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 specifically described 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, halogen atom (eg, fluorine atom, chlorine atom, bromine atom), 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 a chlorine atom is particularly preferable.

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).

[0028]

[Chemical 6]

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 is not coupled 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, and for that purpose, R ₁ and R _At least one of 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.

[0034]

[Chemical 7]

[0035]

[Chemical 8]

[0036]

[Chemical 9]

[0037]

[Chemical 10]

[0038]

[Chemical 11]

[0039]

[Chemical 12]

[0040]

[Chemical 13]

[0041]

[Chemical 14]

[0042]

[Chemical 15]

[0043]

[Chemical 16]

[0044]

[Chemical 17]

[0045]

[Chemical 18]

[0046]

[Chemical 19]

[0047]

[Chemical 20]

[0048]

[Chemical 21]

[0049]

[Chemical formula 22]

[0050]

[Chemical formula 23]

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))

[0052]

[Chemical formula 24]

[0053]

[Chemical 25]

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, further 30 ml of water and 2 ml of concentrated hydrochloric acid.
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))

[0059]

[Chemical formula 26]

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).

[0062]

[Chemical 27]

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%).

Next, the cyan coupler represented by the general formula (III) or (IV), that is, the phenol cyan coupler will be described in detail below.

In the above general formulas (III) and (IV),
R ₁₁ is a linear, branched or cyclic alkyl group having a total carbon atom number (hereinafter referred to as C number) of 1 to 36 (preferably 1 to 24), which may be substituted, and a C number of 6 to 36 (preferably Is an optionally substituted aryl group of 6 to 24) or an optionally substituted heterocyclic group having a C number of 2 to 36 (preferably 2 to 24). Here, the heterocyclic group is a 5- to 7-membered condensed heterocyclic group having at least one hetero atom selected from N, O, S, P, Se and Te in the ring, For example, 2-furyl, 2-thienyl, 4-pyridine,
Examples include 2-imidazolyl and 4-quinolyl. Examples of the substituent of R ₁₁ include halogen atom, cyano group, nitro group, carboxyl group, sulfo group, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group. ,
Arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, or sulfamoylamino group (hereinafter referred to as substituent group A Say)
Is mentioned. The substituent preferably includes a halogen atom (F, Cl, Br, I), a cyano group, an alkyl group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, a carbonamide group or a sulfonamide group.

In the general formula (III), R ₁₁ is preferably an alkyl group, and in the general formula (IV), R ₁₁ is preferably an alkyl group or an aryl group.

In the general formula (III), R ₁₂ is a C number 2
To 36 linear, branched or cyclic alkyl groups. R ₁₂ is preferably an alkyl group having a C number of 2 to 8 (eg ethyl, propyl, isopropyl, t-butyl, cyclopentyl).

In the general formula (III) or (IV),
R ₁₃ is a hydrogen atom, a halogen atom (F, Cl, Br,
I), a linear, branched or cyclic alkyl group having a C number of 1 to 16 (preferably 1 to 8), an aryl group having a C number of 6 to 24 (preferably 6 to 12), and a C number of 1 to 24 (Preferably 1 to 8) alkoxy group, C number is 6 to 24 (preferably 6 to 12) aryloxy group, C number is 1 to 24 (preferably 2 to 12) carbonamide group, or C number is 1.
To 24 (preferably 1 to 12) ureido groups. Here, R ₁₃ is an alkyl group, an aryl group, an alkoxy group,
When it is an aryloxy group, a carbonamido group or a ureido group, it may be substituted with a substituent selected from the above substituent group A.

In the general formula (III), R ₁₃ is preferably a halogen atom, and R ₁₃ in the general formula (IV) is
₁₃ is preferably a hydrogen atom, a halogen atom, an alkoxy group or a carbonamido group, and particularly preferably a hydrogen atom.

In the general formula (III), R ₁₂ and R ₁₃ may combine with each other to form a ring. In addition, the general formula (I
In V), R ₁₃ and R ₁₄ may combine with each other to form a ring. At this time, R ₁₃ may be a single bond or an imino group to serve as a constituent element of the ring.

In the above general formula (IV), R ₁₄ is the above R
₁₁ and synonymous groups, C number alkoxy group having 1 to 36 (preferably 1 to 24), C the number of 6 to 36 (preferably 6 to 24)
Aryloxy group, C number of 1-36 (preferably 1-2)
It is an alkyl- or aryl-substituted amino group of 4).
The R ₁₄ preferably has the same meaning as R ₁₁ , and more preferably an alkyl group.

In the above general formula (III) or (IV), X'represents a hydrogen atom or a coupling-off group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Examples of this coupling-off group include halogen atom (F, Cl, Br, I), sulfo group, C
An alkoxy group of the number 1 to 36 (preferably 1 to 24), C
An aryloxy group having a number of 6 to 36 (preferably 6 to 24), an acyloxy group having a C number of 2 to 36 (preferably 2 to 24), an alkyl or arylsulfonyloxy having a C number of 1 to 36 (preferably 1 to 24) Base, C number 1-36
(Preferably 1 to 24) alkylthio group, C number 6 to 3
6 (preferably 6 to 24) arylthio group, C number of 4 to
36 (preferably 4 to 24) imide group, C number of 1 to 36
A carbamoyloxy group (preferably 1 to 24) or a heterocyclic group (for example, tetrazol-5-yl) bonded to the coupling active position with a nitrogen atom having a C number of 1 to 36 (preferably 2 to 24), pyrazolyl, imidazolyl. , 1, 2,
4-triazol-1-yl). here,
Alkoxy group The following groups may be substituted with a group selected from the above substituent group A. X'is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a sulfo group, an alkoxy group or an aryloxy group, and particularly preferably a hydrogen atom or a chlorine atom.

In the general formula (III) or (IV),
n represents an integer of 0 or 1, and is preferably 0.

Examples of each substituent in the general formula (III) or (IV) are shown below. Examples of R ₁₁ are shown below.

[0076]

[Chemical 28]

[0077]

[Chemical 29]

[0078]

[Chemical 30]

[0079]

[Chemical 31]

Examples of R ₁₂ are shown below.

[0081]

[Chemical 32]

Examples of R ₁₃ are shown below.

[0083]

[Chemical 33]

Examples of R ₁₄ are shown below.

[0085]

[Chemical 34]

[0086]

[Chemical 35]

An example of X'is shown below.

[0088]

[Chemical 36]

[0089]

[Chemical 37]

Specific examples of the cyan coupler represented by the general formula (III) are shown below.

[0091]

[Chemical 38]

[0092]

[Chemical Formula 39]

[0093]

[Chemical 40]

Specific examples of the cyan coupler represented by the general formula (IV) are shown below.

[0095]

[Chemical 41]

[0096]

[Chemical 42]

[0097]

[Chemical 43]

[0098]

[Chemical 44]

[0099]

[Chemical 45]

[0100]

[Chemical 46]

Specific examples of the substituents in the general formula (III) or (IV) other than the above, and the synthesis method of the cyan coupler containing them are described in, for example, US Pat. No. 2,369,992.
No. 9, No. 2772162, No. 2895826,
No. 37772002, No. 4327173, No. 4
No. 333999, No. 4334011, No. 4430
No. 423, No. 4500635, No. 4518687.
No. 4,564,586, No. 4,609,619, No. 4,686,177, No. 4,746,602, JP-A-5
No. 9-164555.

Next, the 1-naphthol type cyan coupler represented by the general formula (V) or (VI) will be described in detail. Q in the general formulas (V) and (VI) represents a mother nucleus coupler residue of a known 1-naphthol type cyan coupler. General formula
R ¹ , R ² , R ³ , R ⁴ , R ⁶ and R in (V) and (VI)
⁶ , t and m are represented by the following general formulas (3-1a) and (3-2)
a), (3-1b), (3-2b), (3-1c) and (3-2c), respectively, as described in detail. These 1-naphthol type cyan couplers have the following general formulas (3-1a), (3-2a), (3-1
b), (3-2b), (3-1c) and (3-2c)
Is represented by

[0103]

[Chemical 47]

In the formula, R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an amino group or an aryl group;
² is a group capable of substituting on a benzene ring, R ³ and R ⁴ are hydrogen atoms, alkyl groups, aryl groups, halogen atoms, alkoxy groups or aryloxy groups, and R ⁵ and R ⁶ are hydrogen atoms, alkyl groups or aryl groups. R ⁷ is a group capable of substituting on the naphthalene ring, Ball is a ballast group, X
Represents a hydrogen atom or a coupling-off group, t represents an integer of 0 to 4, m represents an integer of 0 to 4, and n represents an integer of 0 to 4.

[0105]

[Chemical 48]

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R
⁶ , R ⁷ , Ball, t, and X have the same definitions as in the general formulas (3-1a) and (3-1b), and q is 0 to 0.
The integer of 3 and p are the integers of 0-5, respectively.

[0107]

[Chemical 49]

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R
⁶ , R ⁷ , t, m and p are represented by general formulas (3-1a) and (3-
2a), (3-1b) or (3-2b) has the same meaning as defined above, and Ball ^* represents a coupling-off group which is a ballast group.

In the general formulas (3-1a), (3-1b) and (3-1c), R ¹ is preferably a hydrogen atom or the number of carbon atoms (hereinafter referred to as C number) 1 to 8 (more preferably 1).
To 3) alkyl groups (for example, methyl, ethyl, isopropyl, isobutyl, isoamyl, chloromethyl, fluoromethyl, difluoromethylmethoxymethyl, n-butyl), C2 to 8 (more preferably 2 to 4) alkenyl groups (Eg vinyl, propenyl, allyl), C number 2
8 (more preferably 2 to 4) alkynyl group (eg ethynyl, propargyl), C number 3 to 8 (more preferably 3 to 5) cycloalkyl group (eg cyclopropyl,
2-methylcyclopropyl, 1-methylcyclopropyl, 1-fluorocyclopropyl, cyclobutyl), C
Aralkyl group of number 7 to 12 (preferably 7 to 10) (eg, benzyl, phenethyl), alkoxy group of C number 1 to 8 (preferably 1 to 4) (eg, methoxy, ethoxy)
Alternatively, an amino group having a C number of 0 to 8 (preferably 0 to 4) (for example, amino, methylamino, ethylamino, dimethylamino, pyrrolidyl) or a C number of 6 to 12 (preferably 6)
-10) aryl groups (eg phenyl, p-tolyl,
p-methoxyphenyl, o-tolyl), particularly preferably an alkyl group or a cycloalkyl group.

General formulas (3-1a), (3-2a), (3
-1b), (3-2b), (3-1c) and (3-2)
In c), R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group or an aryloxy group, preferably a hydrogen atom and a C number of 1 to 24 (preferably 1 to 16). ) Alkyl group (for example, methyl, ethyl, isopropyl, n-butyl, n-hexadecyl), C number 6-24 (preferably 6)
To 12) aryl group (eg phenyl group), halogen atom (F, Cl, Br, I), C 1-24 (preferably 1-12) alkoxy group (eg methoxy) or C 6-24 ( It is preferably an aryloxy group of 6 to 12) (for example, phenoxy), and particularly preferably a hydrogen atom or an alkyl group. When t is plural, -CR ³
R ⁴ − may be the same or different.

General formulas (3-1a), (3-2a), (3
-1b), (3-2b), (3-1c) and (3-2)
In c), R ² and R ⁷ are preferably a halogen atom (F, Cl, Br, I) and have a C number of 1 to 12 (preferably 1).
~ 6) alkyl groups (eg methyl, isopropyl, t
-Butyl), a C 3-12 (preferably 3-6) cycloalkyl group (e.g. cyclopropyl, cyclohexyl), a C 1-12 (preferably 1-6) alkoxy group (e.g. methoxy, n-butoxy). ), C number 1 to 12
(Preferably 1 to 6) alkylthio group (eg methylthio, n-dodecylthio), C 6-12 (preferably 6 to 10) aryloxy group (eg phenoxy, p)
-T-butylphenoxy), an arylthio group having a C number of 6 to 12 (preferably 6 to 10), such as phenylthio,
Alkylsulfonyl group having 1 to 12 C (preferably 1 to 6) C (eg methylsulfonyl), arylsulfonyl group having 6 to 12 C (preferably 6 to 10) C (eg p-
Tolylsulfonyl), C number 1 to 12 (preferably 1 to
8) carbonamide group (for example, acetamide, benzamide), C number 1-12 (preferably 1-8) sulfonamide group (for example, methanesulfonamide, p-toluenesulfonamide), C number 1-12 (preferably) 1 to
8) Acyl group (eg acetoxy, benzoyloxy), C number 1 to 12 (preferably 1 to 8) acyloxy group (eg acetoxy), C number 2 to 12 (preferably 2 to 10) alkoxycarbonyl group ( For example, ethoxycarbonyl), a carbamoyl group having a C number of 1 to 12 (preferably 1 to 7) (for example, N-methylcarbamoyl), a sulfamoyl group having a C number of 0 to 12 (preferably 0 to 8) (for example, N-ethylsulfa group). Moyl), a C number 1-12 (preferably 1-8) ureido group (for example, 3-methylureido, 3-phenylureido), a C number 2-12 (preferably 2-10) alkoxycarbonylamino group (for example, Ethoxycarbonylamino), a cyano group, or a nitro group, particularly preferably a halogen atom, an alkyl group,
It is an alkoxy group, an acyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group or a cyano group. Here, when m or q is plural, R ² may be the same or different, and when n or p is plural, R ⁷ may be the same or different. R ² may be substituted at any position of 2 ′, 3 ′, 4 ′ and 5 ′ in the general formulas (3-1a), (3-1b) and (3-1c), but 3 ′ and 4 ′. Alternatively, the 5'position is preferred, and in the general formulas (3-2a), (3-2b) and (3-2c), the substitution may be carried out at any of the 2 ', 3', 5'and 6'positions. Positions of 2'or 6'are preferred. R ⁷ is represented by general formula (3-1a), (3-2a), (3-1b), (3-2
b), 3, 5 in (3-1c) and (3-2c),
Substitution at any of positions 6, 7, and 8 is possible, but position 5, 6, or 7 is preferred.

General formulas (3-2a), (3-2b) and
In (3-2c), R^FiveAnd R⁶Are independent
Represents a hydrogen atom, an alkyl group and an aryl group,
Preferably, a hydrogen atom and a C number of 1 to 24 (preferably 1 to 1)
6) alkyl groups (eg methyl, ethyl, isopropyl)
, N-butyl, n-hexadecyl group), C number 6 to 24
(Preferably 6-12) aryl groups (eg phenyl)
Group, tolyl, naphthyl group). Particularly preferably hydrogen
It is an atom or an alkyl group. Most preferred is R ^FiveOh
And R⁶When at least one of is a hydrogen atom
It

General formulas (3-1a), (3-2a), (3
-1b) and (3-2b), Ball represents a group having a size and a shape sufficient to impart diffusion resistance to the coupler represented by the general formula, and preferably has a C number of 6 to 36.
(More preferably 8 to 24) alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, carbonamide group, sulfonamide group,
Carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, acyl group, acyloxy group, alkylsulfonyloxy group or alkoxycarbonyl group, particularly preferably alkyl group, alkoxy group, aryloxy group, alkylthio group, carbonamido group. , A sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group or an alkoxycarbonyl group. Ball is represented by the general formulas (3-1a) and (3-2a).
At 3, 5, 6, 7, and 8 and the general formula (3-1
b) and (3-2b) may be substituted at any position of 2 ', 3', 4 ', 5', but preferably 5 in the general formulas (3-1a) and (3-2a), The positions 6 and 7 and the positions 3 ′, 4 ′ and 5 ′ in the general formulas (3-1b) and (3-2b).

General formulas (3-1a), (3-2a), (3
-1b) and (3-2b), X represents a hydrogen atom or a coupling-off group capable of being eliminated by a coupling reaction with an oxidized product of an aromatic primary amine developer, preferably a hydrogen atom or a halogen atom. (F, Cl, Br,
I), a sulfo group, a thiocyanato group, an alkoxy group having a C number of 1 to 16 (preferably 1 to 8), an aryloxy group having a C number of 6 to 16 (preferably 6 to 10), and a C number of 1 to 16 (preferably 1-8) alkylthio group, C-number 6-36 (preferably 6-24) arylthio group, C-number 2-16
(Preferably 2 to 12) heterocyclic oxy group, C number 2 to
36 (preferably 2 to 24) heterocyclic thio group, C number 1
To 24 (preferably 1 to 12) acyloxy group, C number of 1 to 24 (preferably 1 to 12) sulfonyloxy group, C number of 2 to 24 (preferably 2 to 12) carbamoyloxy group, C number of 1 To 36 (preferably 1 to 24) azolyl group, C number of 4 to 36 (preferably 4 to 24) imide group, or C number of 3 to 36 (preferably 3 to 16) hydantoinyl group.

As X, a relatively electron-withdrawing group such as a halogen atom, a sulfo group, a thiocyanato group, a heterocyclic thio group, an azolyl group or an imide group is used, and stains (white background stains) are less likely to be generated by light or heat. Is particularly preferable.
In the general formula (Ia) (1b) or (1c), t is preferably 1 or 2, and m, n, p and q are preferably 0 or 1. t is particularly preferably 1,
m, n, p and q are particularly preferably 0.

In formulas (3-1c) and (3-2c), Ball ^* represents a group having a size and shape sufficient to impart diffusion resistance to the coupler, and is an oxidized product of an aromatic primary amine developer. A group capable of splitting off by a coupling reaction with, preferably having a C number of 6 to 36 (more preferably 8 to 2).
4) Alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, heterocyclic thio group, acyloxy group, sulfonyloxy group, carbamoyloxy group, azolyl group, and imide group. Ball ^*
Is particularly preferably an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group or an imido group.

The cyan couplers represented by the general formulas (3-1c) and (3-2c) may be dimers or multimers bound to each other in Ball ^* , and may also be Bal.
It may be a polymeric coupler pendant on the polymer chain (eg polyethylene-like polymer chain, polyester condensation polymer chain) in l ^* . In this case, the range of the number of carbon atoms in Ball ^* may be exceeded. The manner in which such a naphthol-type coupler is bonded to the polymer chain, the type of the copolymerizable monomer or the method of polymerization is described in, for example, US Pat. No. 4,690,889, column 5-
6, JP-A-62-276548, pages 3 to 17, JP-A-1-224756, pages 15 to 42, and EP (EP) 357069A, pages 3 to 10, may be applied. it can.

General formulas (3-1a), (3-2a), (3
-1b), (3-2b), (3-1c) and (3-2)
Among the cyan couplers of the present invention represented by c), the cyan couplers represented by the general formulas (3-1a), (3-1b) and (3-2c) have a small change in hue of a cyan image with time. Is preferred. Hereinafter, the general formula (3-1
a), (3-2a), (3-1b), (3-2b),
Specific examples of the substituents in (3-1c) and (3-2c) are shown below, but the present invention is not limited thereto.

[0119]

[Chemical 50]

[0120]

[Chemical 51]

[0121]

[Chemical 52]

[0122]

[Chemical 53]

[0123]

[Chemical 54]

[0124]

[Chemical 55]

[0125]

[Chemical 56]

[0126]

[Chemical 57]

Hereinafter, the general formula (3-1) or (3-2)
Specific examples of the 1-naphthol type cyan coupler represented by are shown below, but the coupler of the present invention is not limited thereto.

[0128]

[Chemical 58]

[0129]

[Chemical 59]

[0130]

[Chemical 60]

[0131]

[Chemical formula 61]

[0132]

[Chemical formula 62]

[0133]

[Chemical 63]

[0134]

[Chemical 64]

[0135]

[Chemical 65]

[0136]

[Chemical 66]

[0137]

[Chemical 67]

The cyan couplers represented by formulas (V) and (VI) of the present invention are disclosed in JP-A-55-108662.
It can be synthesized by a conventionally known synthesis method including the synthesis method described in the specification.

At least one of the pyrrolotriazole type cyan couplers represented by the general formula (I) or (II) of the present invention (denoted as A) and the general formula (III) of the present invention,
The mixing ratio of at least one cyan coupler represented by (IV), (V) or (VI) (referred to as B) can be arbitrarily set depending on the performance of the photosensitive material. A is preferably 30 mol% or more and 99 mol% or less, more preferably 50 mol% or more and 90 mol% or less. The mixture of the above-mentioned couplers A and B of the present invention is contained in at least the silver halide emulsion layer of the light-sensitive material, but can be added and used in the non-light-sensitive layer adjacent thereto. In the present invention, it is preferably used in a light-sensitive silver halide emulsion layer, and preferably used in a silver halide emulsion layer having red-sensitivity or color sensitivity in the near infrared region.

The amount of the mixture of the couplers A and B of the present invention added to the light-sensitive material is 1 mol of silver in the silver halide emulsion layer, and in the case of the non-light-sensitive layer, 1 mol of silver in the adjacent layer is used.
It is in the range of 1 × 10 ⁻³ to 2 mol per mol. It is preferably in the range of 1 × 10 ^-2 to 1 mol. More preferably 5 ×
It is in the range of 10 ^-2 to 1 mol.

When the layer having a red-sensitive property or a color-sensitive property in the near-infrared region is composed of a plurality of layers, or when it is used as another color-sensitive layer or a non-photosensitive layer in addition to these layers, the present invention The above mixture of A and B couplers can be used for any of these layers, and even if the mixture ratio of A: B is different, the selected coupler of A or B is different. Good. Further, in the case of a plurality of layers, a known cyan coupler different from the coupler of the present invention can be used.

At least one of the pyrrolotriazole cyan couplers represented by the general formula (I) or (II) of the present invention and the general formulas (III) and (IV) of the present invention,
In order to introduce a coupler mixture containing at least one cyan coupler represented by (V) or (VI) into a light-sensitive material, a known dispersion method such as an oil-in-water dispersion method or a latex dispersion method using a high-boiling organic solvent described below is used. Any method can be used. 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 couplers used can be arbitrarily set, but is preferably 3.0 or less,
It is more preferably 2.0 or less. It may also be a dispersion that does not use any high-boiling organic solvent. Regarding the type of the high boiling point organic solvent, the boiling point at atmospheric pressure described below is 17
A compound having a temperature of 5 ° C. or higher can be used.

At least one of the pyrrolotriazole cyan couplers represented by the general formula (I) or (II) of the present invention and the general formulas (III) and (IV) of the present invention,
The use of a coupler mixture consisting of at least one cyan coupler represented by (V) or (VI) retains the excellent performance of individual couplers, and at the same time compensates for the shortcomings of individual couplers and shows better performance. It shows an unexpected effect, and especially color image storability of cyan image, fastness, high color developability (high coupling activity,
(High color density) and excellent color reproducibility.

As the silver halide used in the present invention, silver chloride, silver bromide, silver (iodo) chlorobromide, silver iodobromide and the like can be used. Especially, for the purpose of rapid processing, iodide is used. It is preferable to use a silver chlorobromide or silver chloride emulsion having a silver chloride content substantially free of silver of 90 mol% or more, further 95% or more, and particularly 98% or more. Gelatin usually contains a large amount of calcium ions and is often contained at 5000 ppm or more. Therefore, it is preferable to use deionized gelatin in the present invention. The deionized gelatin used in the present invention preferably has a calcium ion content of 500 ppm or less. Deionized gelatin is preferably used in an amount of 10% by weight or more, and 20% by weight based on the total gelatin.
It is more preferably at least 50% and particularly preferably at least 50%.

In the light-sensitive material according to the present invention, a hydrophilic colloid layer can be decolorized by a treatment described in European Patent EP 0,337,490A2, pages 27 to 76 for the purpose of improving image sharpness and the like. A dye (among others, an oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.70 or more, or a dihydric or tetrahydric alcohol (in the waterproof resin layer of the support) For example, a titanium oxide surface-treated with trimethylolethane etc.
It is preferable to contain 2% by weight or more (more preferably 14% by weight or more).

Photographic additives such as cyan, magenta and yellow couplers which can be used in the present invention are preferably used by dissolving them in a high boiling point organic solvent. The high boiling point organic solvent has a melting point of 100 ° C. or lower and a boiling point of 140 ° C. The above-mentioned water-immiscible compound can be used as long as it is a good solvent for the coupler. The melting point of the high boiling point organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling point organic solvent is preferably 160 ° C. or higher,
More preferably, it is 170 ° C. or higher. Details of these high boiling point organic solvents are described in JP-A No. 62-215272, page 137, lower right column to page 144, upper right column. Further, the cyan, magenta or yellow coupler is impregnated with a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the above high-boiling organic solvent, or is water-insoluble and organic. It can be dissolved with a solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, U.S. Pat. No. 4,857,449, columns 7 to 15
Column and No. 12 of International Publication WO88 / 00723
The homopolymers or copolymers described on pages 30 to 30 are used, more preferably the use of methacrylate-based or acrylamide-based polymers, especially acrylamide-based polymers, in terms of color image stabilization and the like.

That is, European Patent EP 0,27, which chemically bonds with an aromatic amine-based developing agent remaining after color development processing to form a chemically inactive and substantially colorless compound.
Chemical bond with the compound (A) described in No. 7,589A2 and / or the oxidant of the aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound. European Patent EP 0,277,58
The use of the compound (B) described in 9A2 simultaneously or alone prevents, for example, stain generation and other side effects due to the formation of a coloring dye by the reaction of the residual color developing agent in the film or its oxidant with the coupler during storage after processing. It is preferable above.

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.

As the support used in the light-sensitive material of the present invention, a white polyester support for display or a layer containing a white pigment is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to further improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support. In particular, the transmission density of the support is 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferably set in the range of 5 to 0.8.

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.

In exposure, US Pat. No. 4,88
It is preferable to use the band stop filter described in No. 0,726. This removes the light mixture,
Color reproducibility is significantly improved.

The exposed light-sensitive material may be subjected to a conventional black-and-white or color development process, but in the case of a color light-sensitive material, it is preferable to carry out a bleach-fixing process after color development for the purpose of rapid processing. Particularly when the above-mentioned high silver chloride emulsion is used, the pH of the bleach-fixing solution is about 6.5 for the purpose of promoting desilvering.
The following is preferable, and about 6 or less is more preferable.

Silver halide emulsions and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied to the light-sensitive material according to the present invention, and a processing method applied for processing the light-sensitive material. As the additives for treatment and treatment, those described in the following patent publications, particularly European Patent EP 0,355,660A2 (JP-A-2-139544) are preferably used.

[0154]

[Table 1]

[0155]

[Table 2]

[0156]

[Table 3]

[0157]

[Table 4]

[0158]

[Table 5]

Further, as a processing method of a silver halide color light-sensitive material using a high silver chloride emulsion having a silver chloride content of 90 mol% or more, JP-A-2-207250, page 27, upper left column to page 34, upper right. The method described in the section is preferably applied.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[0161]

【Example】

Example 1 As the pyrrolotriazole cyan coupler represented by the general formula (I) of the present invention, 2.0 × 10 ^-2 mol of the coupler of Compound Example (19) was taken, and tricresyl phosphine was used as a high boiling organic solvent. 18.1 g of fate and 20.0 ml of ethyl acetate were added and dissolved, and this solution was added to 200 g of a 10 wt% gelatin aqueous solution containing 1.5 g of sodium dodecylbenzenesulfonate, and the mixture was emulsified and dispersed using a homoblender. The total amount of this emulsion is high silver chloride emulsion 12
3 g (silver 70.0 g / kg emulsion, silver bromide content 0.5 mol%) and coated on a triacetate film base provided with an undercoat layer so that the coated silver amount was 0.65 g / m ² . .. A gelatin layer was applied as a protective layer on the coating layer so that the dry film thickness was 1.0 μm to prepare a sample. As a gelatin hardener, 1-oxy-3,5
-Dichloro-s-triazine sodium salt with gelatin 1
0.02 g was added per g. The sample manufactured as described above is referred to as 101.

Subsequently, the coupler (19) of the present invention was replaced with another coupler in an equimolar amount as shown in Tables 6 and 7, and the weight ratio of tricresyl phosphate as the high boiling point organic solvent to the coupler was changed to Sample 101. Samples 102 to 124 were prepared in the same manner as above, but adjusting to 1.0. The mixing ratio of the sample in which the two couplers were mixed was 1/1. The produced samples 101 to 124 were subjected to gradation exposure of white light (color temperature of light source: 3200 ° K). The exposure at this time was performed so that the exposure amount was 250 CMS in the exposure time of 0.1 seconds. The exposed sample was processed in the next step.

Treatment process Temperature Time Color development 35 ° C 45 seconds Bleach fixing 35 ° C 45 seconds Stability (1) 35 ° C 20 seconds Stability (2) 35 ° C 20 seconds Stability (3) 35 ° C 20 seconds Stability (4) 35 ° C. for 20 seconds Dry 80 ° C. for 60 seconds (Stabilization was a 4-tank countercurrent system from (4) to (1))

The composition of each processing liquid is as follows. [Color developer] Water 800 ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 0.8 ml Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium bromide 0.03 g N, N-diethylhydroxyl Amine 4.6 g Potassium carbonate 27 g Sodium sulfite 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 4.5 g Lithium sulfate (Anhydrous) 2.7 g Optical brightener (4,4'-diaminostilbene type) 2.0 g Water was added to 1000 ml pH (with potassium hydroxide added) 10.25

[Bleach-fixing solution] Water 400 ml Ammonium thiosulfate (700 g / liter) 100 ml Sodium sulfite 18 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 3 g Glacial acetic acid 9 g Water was added to 1000 ml pH 5. Four

[Stabilizer] Benzisothiazolin-3-one 0.02 g Polyvinylpyrrolidone 0.05 g Water was added to 1000 ml pH 7.0.

The cyan color image of the sample obtained by the treatment was subjected to density measurement to obtain a characteristic curve. From this characteristic curve,
The following characteristic values were obtained. (1) Photographic property The logarithmic value of the exposure amount giving the density of the minimum density (Dmin) +0.5 was obtained from the characteristic curve, and the difference (ΔS) from each sample was calculated with reference to Sample 101. A positive value means a high feeling, and a negative value means a low feeling. Further, from the exposure amount giving the density of Dmin + 0.5 on the characteristic curve,
The density value when a high exposure amount of E = 0.4 was given was read, and the density ratio (D%) was obtained with the density of the sample 101 as a reference. The higher the value, the higher the color density.

(2) Color image fastness One sample of the treated and density-measured samples was kept at 100 ° C. for 5 days, and another set was kept at 80 ° C. and 70% RH for 7 days. After storing, the density is measured again, and the density after the test at the exposure amount giving the density 1.5 before the test is read, and the density ratio (D ₁ %) to the density before the test (1.5%) is read. , D ₂ %) and determined as the residual ratio of the color image. The larger the value, the higher the color image fastness.

(3) Color Reproducibility A cyan color image obtained by processing is measured for R density and also for B density, and from these characteristic curves, the exposure amount giving an R density of 1.0 is determined. The respective B concentrations were read, and the difference (ΔD) was determined based on the B concentration of the sample 101 as in the above. The numerical value indicates that the larger the positive value is, the higher the density in the blue light region is, and the absorption that is not preferable for color reproduction, and the larger the negative value is, the more preferable color reproduction is. The obtained results are summarized in Table 6 and Table 7.

[0170]

[Table 6]

[0171]

[Table 7]

[0172]

[Chemical 68]

From the results of the above table, the pyrrolotriazole type cyan coupler represented by the general formula (I) or (II) of the present invention and the general formula (III), (IV) of the present invention,
The combined use with the cyan coupler represented by (V) or (VI) gives high color developability (sensitivity, color density),
Samples 110 to 10 have excellent color image fastness and color reproducibility.
113, 117-120 and comparative samples 101-109, 1
It is clear from comparison with 14 to 116 and 121 to 124. In particular, the color image fastness in the combined use of the pyrrolotriazole cyan coupler represented by the general formula (I) or (II) of the present invention and the cyan coupler represented by the general formulas (III) to (VI) of the present invention It was an unexpected effect that each of them improved compared to the case of using them alone.

Example 2 Based on the sample 110 of Example 1, the couplers (19) and 1C-3 used were replaced with the couplers shown in Tables 8 and 9, respectively, in equimolar amounts. Samples 201 to 2 were prepared in the same manner by adjusting the weight ratio of tricresyl phosphate as an organic solvent and coupler to be constant.
24 was produced. These produced samples were subjected to the same exposure and treatment as in Example 1, and the performance was evaluated in the same manner. The sample 101 of Example 1 was used for the criteria of photographic property and color reproducibility for performance evaluation. The results are also summarized in Tables 8 and 9.

[0175]

[Table 8]

[0176]

[Table 9]

From the results of Table 8 and Table 9, the above-mentioned Example 1 was obtained.
When compared with the above results, it can be seen that the combination of the cyan couplers having the constitution of the present invention gives substantially the same results as the sample of the corresponding combination of Example 1.
Of the pyrrolotriazole couplers represented by the general formula (I) or (II) of the present invention, more specifically, the coupler represented by the general formula (I) is represented by the general formula (II). Samples 201 to 206 and Samples 210 to 212 and Samples 207 to 209 and Sample 2 are superior in photographic property, color image fastness and color reproduction as compared with the coupler.
It is clear from comparison with 13, 214.

Example 3 The surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, followed by providing a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and further coating various photographic constitutional layers to give A multilayer color photographic paper (301) having the layer structure shown was produced. The coating liquid was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cod-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-6) 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 liquid for fifth layer Cyan coupler (ExC) 30.0 g, ultraviolet absorber (UV-2) 18.0 g, color image stabilizer (Cod-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-3) 45.0 g and solvent (Solv-1) 2.0 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 emulsified dispersion C was prepared by emulsifying and dispersing with an ultrasonic homogenizer. On the other hand, silver chlorobromide emulsion C (cube, average grain size 0.50
Large size emulsion C of μm and small size emulsion C of 0.41 μm
1: 4 mixture with (Ag molar ratio). The coefficient of variation of the grain size distribution was adjusted to 0.09 and 0.11, respectively, and for each size emulsion, 0.8 mol% of AgBr was locally contained in a part of the grain surface). In this emulsion C, the red sensitizing dye E shown below was 0.9 × 10 ⁻⁴ mol for the large size emulsion C per mol of silver and 1.1 × 10 ^{4 for} the small size emulsion C. ^-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 Emulsion C was carried out by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion C and this red-sensitive silver chlorobromide emulsion C were mixed and dissolved, and a fifth layer coating solution was prepared so as to have the composition shown below.

The coating solutions for the second to fourth layers, the sixth layer and the seventh layer 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. In addition, the total amount of Cpd-14 and Cpd-15 in each layer is 25.0.
It was added at a concentration of mg / m ² and 50 mg / m ² . The spectral sensitizing dyes used in the silver chlorobromide emulsion of each photosensitive emulsion layer are as follows.

[0182]

[Table 10]

[0183]

[Table 11]

[0184]

[Table 12]

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.

[0186]

[Chemical 69]

(Layer Structure) 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.

[0188]

[Table 13]

[0189]

[Table 14]

[0190]

[Table 15]

[0191]

[Table 16]

[0192]

[Chemical 70]

[0193]

[Chemical 71]

[0194]

[Chemical 72]

[0195]

[Chemical formula 73]

[0196]

[Chemical 74]

[0197]

[Chemical 75]

[0198]

[Chemical 76]

[0199]

[Chemical 77]

The sample manufactured as described above is referred to as 301. Subsequently, Samples 302 to 308 were prepared by replacing the cyan coupler ExC used in the fifth layer (red-sensitive emulsion layer) of Sample 301 with an equimolar amount as shown in Table 17.

After imagewise exposure of the above-mentioned light-sensitive material, continuous processing (running test) was carried out until performance was replenished by using a paper processor until the tank capacity for color development was replenished by 3 times in the following processing steps, and the performance was examined. The samples were processed for Treatment process Temperature Time Replenisher ^* Tank capacity Color development 38.5 ° C 45 seconds 73 ml 5 liters Bleach fixing 35 ° C 45 seconds 60 ml ^** 5 liters Rinse (1) 35 ° C 30 seconds-5 liters Rinse (2) 35 ° C 30 Second-5 liters Rinse (3) 35 ° C 30 seconds 360 ml 5 liters Dry 80 ° C 60 seconds * Replenishment amount per 1 m ^{2 of} light-sensitive material ** In addition to the above 60 ml, rinse (1) per 1 m ^{2 of} light-sensitive material 120 ml was poured. (Rinse was a three-tank countercurrent system from (3) to (1))

The composition of each processing liquid is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Ethylenediaminetetraacetic acid 3.0 g 3.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g 0.5 g Triethanolamine 12.0 g 12.0 g Potassium chloride 6.5 g-Potassium bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX 4 manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 3.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis (sulfur Honatoethyl) hydroxylamine 5.0 g 10.0 g Triisopropylnaphthalene (β) sodium sulfonate 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfur Acid ・ monohydrate 5.0g 11.5g Add water 1000ml 1000ml pH (25 ℃ / potassium hydroxide and (With sulfuric acid) 10.00 11.00

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Water 600 ml 150 ml Ammonium thiosulfate (700 g / l) 100 ml 250 ml Ammonium sulfite 40 g 100 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g 135 g Ethylenediaminetetraacetic acid 5 g 12.5 g Ammonium bromide 40 g 75 g Nitric acid (67%) 30 g 65 g Water was added 1000 ml 1000 ml pH (25 ° C / acetic acid and aqueous ammonia) 5.8 5.6

[Rinse Solution] (Same as tank solution and replenisher) Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

The processed sample was subjected to concentration measurement for each of B, G and R. From the obtained characteristic curve, the R density was evaluated in terms of photographic properties (sensitivity, color density) in the same manner as in Example 1, and the color image fastness and color reproducibility were also measured in the same manner as in Example 1. For color image fastness, use a xenon fading tester (illuminance 9
It was exposed to light for 10 days using 10
It was examined by the same method as the evaluation of fastness at 0 ° C.) and wet heat (80 ° C., 70% RH). The photographic properties and color reproducibility were evaluated with reference to Sample 301. The results are shown in Table 17.

[0206]

[Table 17]

From the table, the pyrrolotriazole type cyan coupler represented by the general formula (I) or (II) of the present invention and the general formula (III) or (IV) or (V) of the present invention are shown.
It was confirmed that when used in combination with the cyan coupler represented by the formula (VI), excellent color forming properties (sensitivity, color density), excellent color image fastness and color reproducibility were exhibited.

Example 4 Sample 302 described in JP-A-2-854 and Example 3 was prepared according to the method described. Subsequently, the cyan coupler Ex used in the third layer and the fourth layer of the same sample 302, Ex
Among C-1, -2 and -3, ExC-3 is replaced with an exemplary coupler (3) of the coupler represented by the general formula (I) of the present invention, and ExC-1 / ExC-2 / (3) = 1 /
A sample 401 was prepared by replacing it so that the ratio became 1/2 (molar ratio). The total amount of the coupler used was applied so as to be equimolar to Sample 302. Further, a sample 402 was prepared by substituting the exemplary coupler (3) of the present invention used in the sample 401 with the exemplary coupler (16) of the present invention in an equimolar amount. These samples were cut and then subjected to wedge exposure with a three-color separation filter.
No., Example 3 is used for continuous processing until the cumulative replenishment amount of the color developing solution is replenished by 3 times the tank capacity by using an automatic processor, and then the sample for performance evaluation is treated. It was

With respect to the cyan color image of the sample obtained by the processing, the same performance evaluation as in Example 3 was conducted. As a result, a sample 401 prepared by combining the pyrrolotriazole cyan coupler represented by the general formula (I) or (II) of the present invention with the cyan coupler represented by the general formulas (III) and (IV) of the present invention, and 402 is Japanese Patent Laid-Open No. 2-854
It was confirmed that the sample was provided with higher sensitivity and color density than the sample 302 of Example 3 of No. 3, and was excellent in color image fastness and color reproducibility. It was found that the color image fastness was particularly excellent.

Example 5 Using the samples 101 to 105 produced in Example 1 and the samples 301 to 308 produced in Example 3, the following performances were examined. (1) Color developability (a) A red separation filter is attached to the front surface of the wedge to perform exposure under the same exposure conditions as in Example 1, and imagewise exposure is separately performed before the continuous processing of the color development processing used in Example 3 is started. A given sample was run until it was replenished with 5 times the capacity of the color developing tank, and then the sample was tested for performance. The processed sample was subjected to concentration measurement, and the sensitivity and the concentration were obtained by the same method as in Example 1, and the sensitivity difference (ΔS ₁ ) and the concentration ratio (D ₁ %) was calculated. (b) Next, using a solution in which a part of the composition of the color developing solution used in the color developing treatment was changed as follows, the replenisher amount was set to 40 ml / m ² and color developing was performed at 40 ° C. for 45 seconds. Same as above, but after carrying out the running process, the sensitivity and concentration were obtained in the same manner, and the sensitivity difference (ΔS ₂ ) between the same samples based on the value of the sample at the start of continuous processing performed in (a) above as a reference , And the concentration ratio (D ₂ %) was calculated.

Color developer (only changed parts are shown) Tank solution Replenisher Ethylenediaminetetraacetic acid 3.0 g 5.0 g Triethanolamine 12.0 g 15.0 g Potassium chloride 8.0 g-g Fluorescent brightener (WHITEX 4 Sumitomo Chemical Co., Ltd.) 1.0 g 5.0 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 5.0 g 15.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4 -Aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 18.0 g pH 10.2 g 12.2 g

(2) Color Reproducibility The R and B concentrations of these samples were measured using the continuously treated samples of (a), which were carried out to investigate the above-mentioned color development, and then 60 ° C. and a relative humidity of 70. % Of the sample was stored for 2 months and the concentration was measured again. From these characteristic curves, the B density at the point of the exposure amount that gives the R density of the minimum density +2.0 before the test is read, and the B density at the point of the same exposure amount after the test is also read, and the high temperature and high temperature are read. The increase in the yellow density in the cyan density when the color image was stored under the humid condition was examined and set as one of the evaluations of the color reproducibility.

The results are shown in Table 18.

[0214]

[Table 18]

From Table 18, Samples 302 to 308 satisfying the constitutional requirements of the present invention showed more stable color development in continuous processing than Comparative Samples 101 to 105 and 301, and the factors of color development processing were changed to obtain a low replenishing amount. Good color development is exhibited even when color development processing is performed. In addition, even if the color image is stored for a long time under the conditions of high temperature and high humidity, the hue change due to the increase of the yellow component of the cyan color image is small, giving excellent color image storability,
Color reproducibility can be retained in an excellent manner. In particular, the pyrrolotriazole-based cyan coupler of the present invention and the general formula (III)
~ (VI) by using in combination with the cyan coupler represented by the above color development, color reproducibility,
It is surprising that the color image storability is excellent.

[0216]

The above-mentioned general formula (I) or (II) of the present invention
When a pyrrolotriazole-based cyan coupler represented by the above general formulas (III), (VI), (V) and (VI) of the present invention are used in combination, the color image fastness is
A silver halide color photographic light-sensitive material having excellent color reproducibility and high color development can be provided.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer is a pyrrolotriazole represented by the following general formula (I) or (II). At least one cyan cyan coupler and the following general formulas (III), (IV),
A silver halide color photographic light-sensitive material containing at least one cyan coupler represented by (V) or (VI). [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. ) [Chemical 2] In formulas (III) and (IV), R ₁₁ represents an alkyl group, an aryl group or a heterocyclic group, R ₁₂ represents an alkyl group having 2 or more carbon atoms, and R ₁₃ represents a hydrogen atom, a halogen atom or an alkyl group. , An aryl group, an alkoxy group, an aryloxy group, a carbonamido group or a ureido group, R ₁₄ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group or an amino group, and X ′ represents hydrogen. An atom or a group capable of splitting off in a coupling reaction with an oxidation product of an aromatic primary amine color developing agent, and n represents 0 or 1. General formula (III)
R ₁₂ and R ₁₃ may combine with each other to form a ring, and R ₁₃ and R _{14 in} formula (IV) may combine with each other to form a ring. In the general formulas (V) and (VI), Q represents a naphthol mother nucleus coupler residue bonded at the 2-position, R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an alkoxy group. Represents a group, an amino group or an aryl group, R ² represents a group capable of substituting for a benzene ring, R ³ and R ⁴ represent a hydrogen atom, an alkyl group,
Represents an aryl group, a halogen atom, an alkoxy group or an aryloxy group, R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group or an aryl group, t represents an integer of 0 to 4, and m represents an integer of 0 to 4. Represent.