JPH03289654A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain excellent color reproducibility by incorporating one kind of specific cyan couplers and two kinds among three specific compds. into the above photosensitive material. CONSTITUTION:At least one kind of the cyan couplers expressed by formula I and at least two kinds of the compds. expressed by formula II, formula III and formula IV are incorporated into this photosensitive material. In the formula I, R1, R2 respectively denote an org. group bonding to an imidazole ring via a carbon atom, nitrogen atom, etc.; X denotes a hydrogen atom or the group which is eliminated by reaction with an oxidant. In the formula II, R3, R4 respec tively denote a hydrogen atom, alkyl group, etc.; R5, R6 respectively denote a halogen atom, alkyl group, etc.; m, n respectively denote 0 to 4 integer; A denotes a bivalent combination group. In the formula III, R7 denotes an aliphat. group, aryl group; Y denotes the nonmetal atom group necessary for forming 5- to 8-membered heterocycles together with a nitrogen atom. In the formula IV, R13 denotes a hydrogen atom, alkyl group, etc.; R8 to R12 respectively denote a hydrogen atom, alkyl group, etc. The excellent color tone reproducibility approximate to the color tones of printing ink is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material having excellent color reproducibility and image storage stability.

[Background of the Invention] Silver cohalide color photographic materials generally use so-called dye-forming couplers that react with a light-sensitive silver halide emulsion and an oxidized color developing agent to form a dye.

Among these, phenols or naphthols have been widely used as cyan couplers, and these include, for example, rice! iI Patent No. 2.369.929, No. 2
．． 423.730, 2,474,293, 2.772.162, 2,8
It is described in specifications such as No. 95,826 and JP-A-56-65134.

However, cyan dye images obtained from phenols and naphthols have had serious problems in color reproduction. In other words, these cyan color-forming dyes have poor absorption spectrum on the short wavelength side, and have unnecessary absorption, that is, asymmetric absorption, in the green portion and some blue portions. To solve this problem, conventional negative films have been corrected for asymmetric absorption by masking with colored couplers, but this is undesirable as it causes a decrease in sensitivity, and in the case of reversal sensitive materials and color papers, correction Currently, there is no means to do so, and color reproducibility is considerably deteriorated.

As one of the technologies to solve this problem, the first British patent
Examples include couplers having a diphenylimidazole core described in No. 545,507.

Dyes formed from this coupler are not preferred because they have sharp absorption or require a mordant for stabilization, and the developing agent is an amine phenol. or,
An example using phenylenediamine as a developing agent has also been proposed by European Patent No. 249.453. The dye formed from this coupler has the advantages of sharp absorption, little irregular absorption in the green area, and a large molecular extinction coefficient, but it has sufficient image storage stability and poor light fastness. Therefore, it has not yet been put into practical use.

Recently, silver halide color photographic materials (hereinafter referred to as silver
A proofreading system (so-called color proofing) using a color photosensitive material is being used.

When using a color photosensitive material (color vapor) as a color proof, the monochromatic color formed from yellow, magenta, and cyan couplers has a different tone from the yellow, magenta, and cyan of the printing ink, so the colors of the printing ink can be faithfully reproduced. It is difficult to

A dye formed from a coupler having a diphenylimidazole core has sharp absorption, is close to the cyan color of printing ink, and can be reproduced at a good level, but its light resistance is extremely poor, so it cannot be put to practical use as a color proof. It was difficult.

[Object of the Invention] The present invention has been made in view of the above-mentioned circumstances, and the first object of the present invention is to provide a cyan dye image with sharp spectral absorption, less irregular absorption, and excellent color reproducibility. An object of the present invention is to provide a silver halide color photographic material.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material in which cyan dye images have excellent light fastness.

A third object of the present invention is to provide a color photosensitive material that has color tone reproducibility similar to that of printing ink and has improved light fastness.

[Structure of the Invention] The above object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which a cyan coupler represented by the following formula (C-I) is provided. and at least one of the following -I], general formula [A-
I:], -I], general formula [A-I[) and -mathematical formula [A-
It is distantly related to silver halide color photographic materials characterized by containing at least two of the compounds represented by [).

- Formula (C-I) [wherein RI and R2 each represent an organic group bonded to the imidazole ring via a carbon atom, nitrogen atom, oxygen atom, or sulfur atom, and X is a hydrogen atom or a color developing agent (General formula CA-I) General formula (A-n) representing a group that can be separated by reaction with an oxidant of Or represents an aryl group. R5 and R6 are each a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acylamino group, a sulfonyl group, a sulfonamide group, or a hydroxy group. 0m and n each represent an integer from 0 to 4, and when m is an integer from 2 to 4, each R5 may be the same or different, or 7':n is 2 When the Il number is ~4,
Each R6 may be the same or different,
A represents a divalent linking group,] [wherein R7 is an aliphatic group,
represents an aryl group, and Y represents a group of nonmetallic atoms necessary to form a 5- to 8-membered heterocycle with a nitrogen atom.] General formula A-111) IO [wherein RI3 is a hydrogen atom, an alkyl group, cycloalkyl group, alkenyl group, aryl group, hete\R13... R,, l+ and R,, +11 may be the same or different from each other, and each represents an alkyl group, alkenyl group, aryl group, alkoxy group, Represents an alkenoxy group or an aryloxy group.

Rs, Rs, R+o, R8 and R12 may be the same or different, and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an acylamino group, a sulfonamide group, an alkylamino group,
Represents an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom or -OR+4. Here, RI4 represents the same group as the group represented by R12, and R13 and Rs may be combined with each other to form a 5jii ring, a 6-membered ring, or a spiro ring,
R8 and Rs or Rs and R0 may be bonded to each other to form a 5-membered ring, and the 6-membered ring may form a spiro ring. The present invention will be explained in detail below.

In the cyan coupler represented by the general formula [C-I] according to the present invention, R7 and R2 each represent an organic group bonded to the imidazole ring via a carbon atom, nitrogen atom, oxygen atom or sulfur atom.

X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of a color developing agent.

The organic group bonded to the imidazole ring via the carbon atom represented by R1 and R2 above includes an alkyl group (for example,
Methyl group, i-propyl group, 1-butyl group, trifluoromethyl group, benzyl group, 3-(4-aminophenyl)
propyl group, allyl group, 2-dodecyloxyethyl group,
3-phenoxypropyl group, 2-hexylsulfonylethyl group, 3-(4-(4-dodecyloxybenzene)sulfonamidophenyl]propyl group, l-methyl 2-
((2-octyloxy-5-t-octylphenyl)
Sulfonamidophenyl]ethyl group, 1-methyl-2-
[2-octyloxy-5-(2-octyloxy-5
-t-octylphenylsulfonamide) phenylsulfonamide] ethyl group, 2-[2-octyloxy-5
-(2-octyloxy-5-t-octylphenylsulfonamide) phenylsulfonamide] ethyl group, etc.)
, aryl group (e.g. phenyl group, naphthyl group, 2,
4-dichlorophenyl group, 2-hydroxy-5-methylphenyl group, 2-acetamidophenyl group, 2-methanesulfonamidophenyl group, 2-butanamidophenyl group, 2-(N,N-dimethylsulfamoylamino)
Phenyl group, 2-(4-dodecyloxybenzenesulfonamido)phenyl group, 2-[2-<2.4-di-t
-amylphenoxy)hexaneamide] phenyl group, 2
-(2-octyloxy-5-t-octylphenylsulfonamide> phenyl group, 4-carbamoylphenyl group, 4-cyanophenyl group, 4-carboxyphenyl group, 4-ethoxycarbonylphenyl group, etc.), heterocyclic group (
Examples include 4-pyridyl group, 2-benzimidazolyl group, etc.), cyano group, carboxyl group, acyl group, carbamoyl group, alkoxycarbonyl group, and aryloxycarbonyl group.

Examples of the organic group bonded to the imidazole ring via a nitrogen atom include an acylamino group (e.g., acetamide group, benzamide group, 2.4-di-t-amylphenoxyacetamide group, 2.4-dichlorobenzamide group, etc.), alkoxy Carbonylamino group (e.g., methoxycarbonylamino group, propoxycarbonylamino group, t-butoxycarbonylamino group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group)
, sulfonamide group (e.g., methanesulfonamide group, octane sulfonamide group, benzenesulfonamide group, 4-dodecyloxybenzenesulfonamide group, etc.)
, anilino group (e.g., phenylamino group, 2-chloroanilino group, 2-chloro-4-tetradecanamide anilino group, etc.), ureido group (e.g., N-methylureido group, N-butylureido group, N-phenylureido group) basis,
N,N-dibutylureido group, etc.), sulfamoylamino group (e.g., N,N-diethylsulfamoylamino group, N-phenylsulfamoylamino group, etc.), amino group (e.g., unsubstituted amino group, N-methylamino, N,
N-diethylamino group, etc.), heterocyclic group (for example, 3,5
-dimethyl-1-pyrazolyl group, 2,6-dimethylmorpholino group, etc.).

Examples of the organic group bonded to the imidazole ring via an oxygen atom include an alkoxy group (e.g., methoxy group, ethoxy group, i-propoxy group, butoxy group, 2.2.2-) trifluoroethoxy group, 3.3° 3-trifluoropropoxy group, 2-chloroethoxy group, 2-cyanoethoxy group,
2-butanesulfonylethoxy group, etc.), aryloxy group (e.g., phenoxy group, 4-methoxyphenoxy group, 2,4-dichlorophenoxy group, 4-(2-ethylhexanamido)phenoxy group, etc.), silyloxy group ( For example, trimethylsilyloxy group, dimethylphenylsilyloxy group, dimethyl-t-butylsilyloxy group, etc.), heterocyclic oxy group (for example, tetrahydropyranyloxy group, 3-pyridyloxy group, 2-(1,3-benzimidazolyl group), ) oxy group, etc.).

Examples of the organic group bonded to the imidazole ring via a sulfur atom include an alkylthio group (e.g., methylthio group, ethylthio group, butylthio group, 3-[4-(4-dodecyloxybenzene)sulfonamidophenyl]propylthio group, 4- (2-butoxy-5-t-octylphenylsulfonamide)benzylthio group, etc.), arylthio group (e.g., phenylthio group, 2-naphthylthio group, 2,5-
dichlorophenylthio group, 4-dodecylphenylthio group, 2-butoxy-5-t-octylphenylthio group, etc.)
, heterocyclic thio group (e.g. 2-pyridylthio group, 2-(
1,3-benzoxasilyl)thio group, l-hexadecyl-1,2,3,4-tetrazolyl-5-thio group, 1-
(3-N-octadecylcarbamoyl)phenyl-1
, 2,3,4-tetrazolyl-5-thio group, etc.).

Here, at least one of R1 and R2 is preferably an aryl group.

Examples of groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include c, ? Halogen atoms (chlorine, bromine,
fluorine, etc.) and hydroxyl, alkoxy, aryloxy, heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, mercapto, arylthio,
Examples include polygroups such as heterocycle thio, alkoxythiocarbonylthio, acylamino, substituted amino, nitrogen-containing heterocycle bonded by N atom, sulfonamide, alkyloxycarbonyl amino, aryloxycarbonylamino, carboxyl, etc., but preferred are A halogen atom, especially a chlorine atom.

- Among the compounds represented by the formula [C-1), the following are typical compounds - Formulas CC-Ia), [C-Ib] and C
Examples include compounds represented by C-I C].

General formula (C-1a) General formula [C Ib] General formula CC-Ic) In general formula [C-■a] to [C-■C], R21,
R22, R23, R24 and R2S each represent a substituent, L represents an oxygen atom or a sulfur atom, and n is 0 to 5
represents the M number of X has the same meaning as X in the above formula (C-■).

Next, the compound of formula CC-Ia) will be explained in more detail. - In formula CC-Ia), R21 and R
The substituent represented by 22 is not particularly limited, but for example,
Halogen atoms and cyan, nitro, carboxy, alkyl, alkoxy, carbamoyl, sulfamoyl,
Acyl, acyloxy, alkoxycarbonyl, N
HCOR2g, NH3O2R2s, N HCOOR
2G groups can be mentioned. (R26 represents an alkyl group, an aryl group, etc., and R27 represents a hydrogen atom, an alkyl group, an aryl group, etc.. These alkyl groups, aryl groups, etc. may have a substituent.) The above R2+ and R
The alkyl group represented by 22 has 1 to 2 carbon atoms.
A straight or branched alkyl group of 2 is preferable, and examples thereof include a methyl group, an ethyl group, a butyl group, a dodecyl group, and the like. These alkyl groups include cycloalkyl groups such as cyclohexyl groups, and may be substituted.

Preferred substituents include a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a sulfo group, and an alkoxy group having 1 to 22 carbon atoms.

The alkoxy group is preferably a straight or branched alkoxy group having 1 to 22 carbon atoms, such as a methoxy group, an ethoxy group, an i-propyloxy group, an octyloxy group, a dodecyloxy group, and the like. These alkoxy groups are
It may have a substituent.

Examples of the carbamoyl group include unsubstituted alkylcarbamoyl groups such as ethylcarbamoyl group, diethylcarbamoyl group, and dodecylcarbamoyl group; substituted alkylcarbamoyl groups such as butyloxypropylcarbamoyl group and dodecyloxypropylcarbamoyl group; phenylcarbamoyl group; Examples include substituted or unsubstituted arylcarbamoyl groups such as phenylcarbamoyl groups.

Similarly, regarding the sulfamoyl group, unsubstituted alkylsulfamoyl groups such as ethylsulfamoyl group, diethylsulfamoyl group, dodecylsulfamoyl group,
Examples include substituted alkylsulfamoyl groups such as dodecyloxypropylsulfamoyl groups, and substituted or unsubstituted arylsulfamoyl groups such as phenylsulfamoyl groups and various substituted phenylsulfamoyl groups.

In addition, examples of the acyl group include an acetyl group, benzoyl group, butanesulfonyl group, benzenesulfonyl group, etc.; examples of the acyloxy group include &? Acetoxy group, lauroyloxy group, butanesulfonyloxy group, etc.; Examples of the alkoxycarbonyl group include ethoxycarbonyl group, i-propyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, etc.

The N HCOR26 group represents an alkylamide group having 1 to 22 carbon atoms, and representative examples of the unsubstituted alkylamide group include an acetamide group, a butanamide group, a laurylamide group, a stearylamide group, and the like. Further, the alkylamide group may be an alicyclic amide group such as a cyclohexanecarbonamide group, a linear branched structure of a 2-ethylhexaneamide group, or an alkylamide group containing an unsaturated bond. , representative examples of substituted alkylamide groups include halogen-substituted alkylamido groups such as monochloroacetamide group, trichloroacetamide group, perfluorobutanamide group, m-pentadecylphenoxyacetamide group, α-(2,4-di- t-amylphenoxy)pentanamide group, α-(2,4-di-
Examples include phenoxy-substituted alkylamide groups such as a t-amylphenoxy)acetamide group and an 0-chlorophenoxymyristic acidamide group.6 In addition, the -NHCOR2g group represents an arylamide group, and is a representative example of an unsubstituted arylamide group. Typical examples of substituted arylamide groups include alkyl-substituted benzamide groups such as -butylbenzamide group, p-methylbenzamide group, and p-methoxybenzamide group. amide group, alkoxy ilF-converted pennzamide group such as 0-dodecyloxybenzamide group, p-acetamidobenzamide group, m-(2,4
Examples include amide-substituted benzamide groups such as -di-t-amylphenoxyacetamido)penzamide groups, sulfonamide-substituted benzamide groups such as 0-hexadecanesulfonamidebenzamide groups, and p-butanesulfonamidebenzamide groups.

The N HCOOR26 group represents a substituted or unsubstituted alkoxycarbonylamino group having 1 to 22 carbon atoms, and typical examples include an ethoxycarbonylamino group, an i-propoxycarbonylamino group, an octyloxycarbonylamino group, a decyloxycarbonyl group, Examples include methoxyethoxycarbonylamino group.

Further, N HCOOR2g also represents an aryloxycarbonyl group, and a typical example thereof is a phenoxycarbonyl group.

Representative examples include dimethylcarbamoylamino group, diethylcarbamoylamino group, and the like.

-N HS 02 R26 group represents an alkylsulfonamide group or an arylsulfonamide group.

Examples of the alkylsulfonamide group include unsubstituted alkylsulfonamide groups having 1 to 22 carbon atoms such as methanesulfonamide group, butanesulfonamide group, and dodecanesulfonamide group, substituted alkylsulfonamide groups such as benzylsulfonamide group, etc. Examples of the arylsulfonamide group include benzenesulfonamide group, unsubstituted arylsulfonamide group such as naphthalenesulfonamide group, p-toluenesulfonamide group, 2,4.6-1-limethylbenzenesulfonamide group, Examples include substituted arylsulfonamide groups such as alkyl-substituted benzenesulfonamide groups such as p-dodecylbenzenesulfonamide groups, p-dodecyloxybenzenesulfonamide groups, and alkoxy-substituted benzenesulfonamide groups such as butyloxybenzenesulfonamide groups. can.

Formula CC-Id) represents a group represented by the general formula [C-E], and representative examples include dialkylsulfamoylamino groups such as dimethylsulfamoylamino group and dibutylsulfamoylamino group.

Among the compounds represented by the formula CC-Ia), preferred compounds are the following formulas [C-Id) and [C-Ie]
can be mentioned.

In the formula rc-Id and [C-Ie), R2
+, R22, X and n have the same meanings as R2 + , R22, X and n in general formula [:C-Ia), respectively. m represents an integer of 0 to 4. R211 is an alkyl group, an aryl group, -COR26, -5・92R2G, R
2G 502N< .

27 The alkyl group represented by R211 has 1 carbon atom
-32 linear or branched alkyl groups are preferred, and also include cyclohexyl groups such as cyclohexyl groups. Also,
These alkyl groups may be substituted, and representative examples of preferable substituents include A logen atom, hydroxyl group, carboxyl group, cyano group, sulfo group, and alkoxy group having 1 to 22 carbon atoms. can.

The aryl group represented by R29 is preferably a phenyl group, and the phenyl group may be substituted with a nitro group, amide group, sulfonamide group, etc.
NHCOR2S group, -NH3O3R26 group, -NH3
When represented by O3R2g group, R2G and R27 have the same meanings as R2G and R27 in general formula [CIa), respectively.

Among the compounds represented by the formulas CC-Id'l and CC-■e:], a more preferable compound is one in which one of the general formulas is a group represented by -N HR29, and the imidazole ring is Compounds represented by the general formula [CIfl] present at position 0 with respect to

- Formula (C-If) HR29 In the formula, R21, R22, R2l11. X and m have the same meanings as in general formula CCId), and R
29 has the same meaning as R2@. The presence of the -N HR2S group provides better heat resistance as well as absorption of coloring dyes.

Next, the compound of general formula CC-Ib) will be explained in more detail.

In general formula [C-Ib), R22, X and n have the same meanings as R22, X and n in formula CC-Ial, respectively, and R23 and R24 each represent a hydrogen atom, an alkyl group or an aryl group. Also, R2
3 and R24 may be bonded to each other to form a heterocycle.

The alkyl group and aryl group represented by R23 or R24 include the above-mentioned formula (:C-Id) and CC-Ie.
The alkyl groups and aryl groups explained in ] can be specifically mentioned.

The heterocycle formed by combining R23 and R24 is preferably a 5- or 6-membered one, and these heterocycles may have a substituent and may further be fused with a carbocyclic ring (6). Among the compounds represented by C-Ib: ], R1 in the general formula CC-I b ) is more preferable.
One of □ is a group represented by -N HR29, and the general formula [:C
-Ig].

General formula [C-Ig] In the formula, R22, R23, R24 and X are R2°, R23, R2□ and
and R2g and m have the same meanings, respectively, and R211 and m in the above-mentioned formulas CC-Idl and CC-Ie).

Next, the compound of the general formula [C-ICE] will be explained in more detail. - In formula [C-Ic:l, R22, X and n are the same as - R22, X in formula [C-Ia]
and n, respectively, and R25 is a hydrogen atom,
Represents an alkyl group, an aryl group or a heterocyclic group.

Specific examples of the alkyl group and aryl group represented by R2s include the alkyl groups and aryl groups explained in the above-mentioned formulas [C-Id) and CC-Ie).

The heterocyclic group represented by R2S is preferably a 5R or 6-membered one, specifically 2-pyridyl group, 4-pyridyl group, 2-benzimidazolyl group, 3゜5-dimethyl-
Examples include groups such as 1-pyrazolyl group, 4-morpholino group, 3,5-dimethyl-2-furyl group, 2゜4-dimethyl-5-thiazolyl group, and 2-acetamido-4-methyl-5-pyrimidinyl group. .

Among the compounds represented by the general formula [C-Ic), a more preferable compound is one of R22 in the general formula CC-Ic).
Examples include compounds represented by the general formula (C-Ih) in which is a group represented by -NHR29 and present at the 0-position with respect to the imidazole ring.

-Mathical formula [C-Ih:1 In the formula, R22, R2s, L and X are the above-mentioned -Mathical formula [C-Ih:1]
R22, R2S, L and X in C-Ic) have the same meanings, respectively, and R2 and m have the same meanings as the above formula % and m, respectively.

Typical specific examples of cyan couplers used in the present invention are shown below, but the present invention is not limited thereto.

Margin below Compound X 2 Compound 1 NHCOC+Jzs 2 CJ7 (ri H3 NHCOC12H2s aHs C4O.

JslI C4)Is 1 *-CslL + (tl C4H11 CaHs CJt(i) C, H5 Cuhll[t) C5) It l [tl C4H@ CaHs C5H11(t) CaHs NH3OaCeH17 CsL7(t) C+z)I25 0CvH23 Compound 2 C@H17(t) CJL7ft) C6H13[tl CaH+7(tl abs CJ Near ft) C3) 1t(il CaH@0 C6H++ (Sat) NH302CJt7 NH3O2NjCH3iz NHCOCT.

I 2Hs C3Hfu(il aHs J7fil C3)+7 (i) CJ+7ft) Compound [ 1) CJ7fi) Compound 1 F(',) H C3H7(i) 0C+5k3 NHCOOCaHs CJ7(i) The cyan coupler of the present invention is a Hemische-Berichte (C
HeIsche Berichte), 34 volumes,
According to the method described in pages 639-642 (1901), Japanese Patent Application Nos. 61-261488 and 62-13
No. 4144, No. 62-211067, No. 62-227
It can be synthesized according to the method described in No. 476 and the like.

The cyan coupler of the present invention represented by the general formula [C-ll] usually contains 2 x 10-' moles 8 per mole of silver halide.
x ~ 10-1 mol, preferably 1x10-' mol-5X
A range of 10-' moles can be used. The couplers of the present invention can also be used in combination with other types of cyan couplers.

Various methods can be used to incorporate the cyan coupler of the present invention into the silver halide emulsion layer, or the cyan coupler of the present invention can be dissolved and dispersed in a high-boiling organic solvent. An organic solvent may be used alone, or two or more high-boiling point organic solvents may be used in combination, and if necessary, a low-boiling point organic solvent, a water-soluble organic solvent, a polymer compound that is water-insoluble and soluble in an organic solvent, etc. may be used together.

Specifically, the cyan coupler of the present invention is used together with other compounds as necessary, a high boiling point organic solvent is used, a low boiling point and/or water-soluble organic solvent is used as necessary, and/or further as necessary. Depending on the situation, water-insoluble and organic solvent-soluble polymer compounds are simultaneously dissolved, emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, and then added to the desired red-sensitive silver halide emulsion layer. It is preferable.

Examples of high boiling point solvents include phosphoric acid esters, phthalic acid esters, phenol derivatives, which do not react with the oxidized form of the developing agent,
Boiling point 15 of citric acid ester, benzoic acid ester, alkyl amide, fatty acid ester, trimesic acid ester, etc.
Organic solvents having a temperature of 0°C or higher are preferred.

In addition, low boiling point organic solvents used in combination with high boiling point solvents include:
Examples include those having a boiling point of 30 to 150°C, such as ethyl acetate, cyclohexanol, and methyl ethyl ketone.

When the silver halide color photographic light-sensitive material of the present invention is used as a full-color light-sensitive material, a magenta coupler and a yellow coupler are used in addition to the cyan coupler of the present invention. The magenta coupler and yellow coupler at this time are not particularly limited, and those known in the art can be used.

Examples of magenta couplers include 5-pyrazolone series,
Pyrazolobenzimidazole series, pyrazoloazole series,
Open chain acylacetonitrile couplers can be used.

As the yellow coupler, for example, acylacetanilide couplers can be used, and these include benzoylacetanilide and pivaloylacetanilide compounds.

Next, the above-mentioned formula [A-I] will be explained.

In the above formula [A-I], examples of the alkyl group represented by R3 and R4 include linear or branched alkyl groups, such as methyl group, ethyl group, isopropyl group, t-butyl group, and octadecyl group. I can do it. Examples of the cycloalkyl group include a cyclohexyl group, examples of the alkenyl group include an ethynyl group and an allyl group, and examples of the aryl group include a pophenyl group and a naphthyl group.

The halogen atoms represented by R5 and R6 include, for example, fluorine, chlorine, and bromine atoms, and the alkyl groups include, for example, straight chain and branched alkyl groups having 1 to 22 carbon atoms (for example, methyl group, ethyl group, etc.). Isopropyl group, 7-butyl group,
octadecyl group), a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as an allyl group, an aryl group such as a phenyl group,
Naphthyl group, alkoxy group such as methoxy group, ethoxy group, dodecyloxy group, aryloxy group such as phenoxy group, naphthoxy group, alkylthio group such as methylthio group, dodecylthio group, arylthio group, etc. Examples of the group include a phenylthio group, examples of the acylamino group include an acetamido group and a benzamide group, examples of the sulfonamide group include a methanesulfonamide group and a benzenesulfonamide group, and examples of the acyl group include an acetyl group, Examples of the benzoyl group and the sulfonyl group include a methanesulfonyl group and a pencenesulfonyl group.

The groups listed above may each be substituted with other substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, aryloxy groups, hydroxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, alkylamino groups, arylamino groups, acylamino groups, and carbamoyl groups. , a sulfonamide group, a sulfamoyl group, and the like.

A represents a divalent linking group, specifically an alkylene group, Rts Rts -5O2-5-S-1-CON-15O2N-R+ s
RIs R+ 5N-5
02N-Co --N-.

R111 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a phenyl group, respectively.

Further, the above alkylene group may have one or more substituents, and examples of the substituents include an aryl group, a cyano group, a halogen atom, a heterocyclic group, a cycloalkyl group, and an alkoxy group. , hydroxy group, aryloxy group, etc.

The alkylene chain itself may constitute a cycloalkyl ring, as in

Typical specific examples of these compounds are shown below, but the compounds used in the present invention are not limited thereby.

■ 4 ■-13 ■-14 ■-15 ■-16 Ca) Is C4H9(i) ■ ■ ■ ■-10 ■ One-20 ■ 1 H3 H3 H3 C3H7(i) H H3 CH3 CH3 ! j! C4Hg L41'I9 CH2 CH3 CH3 CH3 3H7 CH3CH3 Next, the compound represented by the formula [A-III will be specifically explained.

In the above formula [A-ff], R7 represents an aliphatic group and an aryl group.

The aliphatic group may be linear, branched, or cyclic. Further, these aliphatic groups may be saturated or unsaturated, and furthermore, these aliphatic groups may have a substituent.

Examples of saturated aliphatic groups include methyl, ethyl, butyl, octyl, dodecyl, tetradecyl, and hexadecyl groups, and examples of unsaturated aliphatic groups include ethynyl and propenyl groups.

Examples of the cyclic aliphatic group include a 5- to 7-membered cycloalkyl group (eg, cyclopentyl, cyclohexyl group) which may have a substituent.

Examples of the aryl group include pophenyl group and naphthyl group.

Moreover, these aryl groups may have a substituent.

Examples of substituents for the aliphatic groups and aryl groups include alkyl, aryl, alkoxy, carbonyl, carbamoyl, acylamino, sulfamoyl, sulfonamide, carbonyloxy, alkylsulfonyl, arylsulfonyl, hydroxyl, heterocycle, alkylthio,
Examples include multiple groups such as arylthio, and these substituents may further have a substituent.

In the general formula [A-n], Y together with the nitrogen atom is 5 to 8
Represents a group of nonmetallic atoms necessary to form the heterocycle of R.

It is preferred that the heterocycle has at least two heteroatoms, in which case it is preferred that the at least two heteroatoms are not adjacent to each other.

Examples of the 5- to 8-membered heterocycle formed by Y include pyrrolidine, piperidine, piperazine, morpholine, pyridine, thiamorpholine, imidazolidine, homopiperazine, and 4-sulfopiperidine.

Further, the heterocycle may have a substituent, and examples of the substituent include an alkyl group and an aryl group. An aromatic ring such as a benzene ring may be fused to the heterocycle.

Furthermore, cases where the carbon atom in the heterocycle is a spiro carbon atom are also included in the present invention.

Among the compounds represented by the general formula [A-III, preferred are the compounds represented by the following formula [A-I[al].

General formula [A-I[al] In the formula, R and o represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a bridged hydrocarbon group, an alkylsulfonyl group, or an arylsulfonyl group. , R21 represents a group that can be substituted on the benzene ring 4m
represents an integer from 0 to 4. When m is 2 or more, multiple R3
1 may be the same or different, and R3 and comrades may form a ring.

Y' represents a nonmetallic atom group having the same meaning as Y in the general formula [A-II].

In the formula [A-IIa] above, the alkyl group represented by R30 is a straight or branched alkyl group having 1 to 24 carbon atoms (e.g. methyl, ethyl, isopropyl, 7-butyl, 2-ethylhexyl, dodecyl, t-octyl, benzyl group, etc.) are preferred.

As a cycloalkyl group, a cycloalkyl group having 5 to 24 carbon atoms (for example, cyclopentyl, cyclohexyl group, etc.)
is preferred.

As an alkenyl group, an alkenyl group having 3 to 24 carbon atoms (
For example, allyl, 2,4-pentagenyl, etc.) are preferred.

Examples of the aryl group include phenyl and naphthyl groups.

Examples of the heterocyclic group include pyridyl, imidazolyl, and thiazolyl groups.

Examples of the acyl group include polyacetyl and benzoyl groups.

Examples of the bridged hydrocarbon group include bicyclo [2°2.1
1-heptyl group and the like.

Examples of the alkylsulfonyl group include dodecylsulfonyl and hexadecylsulfonyl groups, and examples of the arylsulfonyl group include phenylsulfonyl.

These polygroups include those having further substituents, for example, substituents for polyalkyl groups include halogen atoms, hydroxyl, alkoxy, aryl, acylamino, sulfonamide, aryloxy, alkylthio, carbamoyl, sulfamoyl, alkylsulfonyl, Examples include multiple groups such as nitro, cyano, arylsulfonyl, carboxyl, amine, arylamino, alkylamino, alkoxycarbonyl, acyl, and acyloxy, and substituents for the group represented by R3° other than alkyl include the above-mentioned substituents. and alkyl groups.

Preferred R3o is an alkyl group.

Groups that can be substituted on the benzene ring represented by R31 are not particularly limited, but representative examples include halogen atoms, alkyl, aryl, alkoxy, aryloxy,
alkylthio, arylthio, acyl, acylamino,
Sulfonamides (e.g. alkylsulfonamides, arylsulfonamides, etc.), alkoxycarbonyls, carbamoyls (e.g. alkylcarbamoyls, arylcarbamoyls, etc.), ureidos (e.g. alkylureidos, arylureidos, etc.), sulfamoyls (e.g. alkylsulfamoyls, arylsulfonamides, etc.) sulfamoyl, etc.), amino (including yr1 amino), sulfonyl, nitro, cyano, carboxyl, etc. Among these, preferred as R31 are halogen atom, alkyl group, alkylthio group, acylamino group, It is a sulfonamide group.

The group represented by R3+ may further have a substituent.

m represents an integer of 0 to 4, preferably 0 to 2
When m is 2 or more, R3, may be the same or different, and R31 may form a ring together. Also R 3I
may be combined with -0R3o to form a ring.

-1 f-2 It can be in the para position, but preferably in the para position.

Representative examples of compounds represented by the general formula [An] are shown below, but the present invention is not limited to these compounds.

Below margin f-3 I-4 I-5 1-6 I[-7 ll-8 CH3 CH3 CH3 l-12 ■-19 ■ 0 ■-23 ■-24 ℃--ノ ■-13 ■-14 ■ 5 ■-16 CI SH3 2Hs 2H6 ■-18 ■ 5 ■ 6 ■ 7 ■-28 2H5 ■-29 CH3 It-30 ■-31 C12H2! i ■-32 ■-33 ■-34 l-40 ■-41 ■-42 1 ■ 3 ■-44 N ■-45 ■-35 ■-37 C) 13 ■-39 C@H+7 (tl ■ 7 ■- 48 ■-49 ■-53 ■-55 ■-62 ■-63 ■-65 ■-66 H3 ■-57 ■-59 ■-60 ■-61 ■-67 ■ 8 ■-69 ■-70 1 j Below margin Next, the compound represented by the general formula [A-1[[] will be specifically explained.

The alkyl group represented by the general formula [A-11[col 0 R13] has 1 to 2 carbon atoms.
4 straight-chain or branched alkyl groups, such as methyl, ethyl, i-propyl, t-butyl, octyl, 2-ethylhexyl, dodecyl, tetradecyl, hexadecyl, eicosyl, benzyl, and the like.

The cycloalkyl group represented by R13 has 5 carbon atoms.
to 24 cycloalkyl groups, such as cyclopentyl,
Examples include multiple groups such as cyclohexyl.

Examples of the alkenyl group represented by R12 include alkenyl groups having 2 to 24 carbon atoms, such as polygroups such as ethynyl, propenyl, butenyl, octenyl, decenyl, and oleyl.

Examples of the aryl group represented by RI3 include a phenyl group and a naphthyl group.

The heterocyclic group represented by R+1 is preferably a 5- to 8-membered ring, such as pyrrolidinyl, piperidyl, piperazinyl, morpholinyl, pyridyl, thiamorpholinyl, imidazolidinyl, thiazolidinyl, homopiperazinyl, 4-
Examples include multiple groups such as sulfopiperidyl.

Examples of the alkyl group, alkenyl group, and aryl group represented by R13" and R13"' include the same groups as explained for R12, and the alkyl and alkenyl groups constituting the alkoxy group, alkenoxy group, or aryloxy group. Alternatively, the aryl component is also the same as that described for R+3.

Examples of the alkyl group, cycloalkyl group, alkenyl group, and aryl group represented by Re, Rs + Rlo, R++, and R112 include the same groups as those explained for R13 above.

Examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms.

Examples of the acylamino group include groups such as acetylamino and benzoylamino.

Examples of the sulfonamide group include groups such as methylsulfonylamino and benzenesulfonylamino.

The alkyl component constituting the alkylamino group and the alkylthio group includes the same alkyl groups as mentioned above.

Examples of the aryl component constituting the arylthio group include the same as the aryl group described above.

Examples of alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, and benzyloxycarbonyl groups; and aryloxycarbonyl groups include:
For example, a phenoxycarbonyl group can be mentioned.

In the general formula [A-1[], among the substituent groups, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or a group having even a partial group thereof further has a substituent. It's okay.

For example, substituents for alkyl or cycloalkyl groups include halogen atoms and hydroxyl, alkoxy, alkylthio, acylamino, sulfonamide, aryl,
Aryloxy, carboxyl, amino, alkylamino, awaramino, carbamoyl, sulfamoyl,
Examples include multiple groups such as alkylsulfonyl, arylsulfonyl, nitro, cyano, alkoxycarbonyl, acyl, and acyloxy.

Examples of substituents for groups other than alkyl groups include the above-mentioned substituents and alkyl groups.

Further, as substituents that the aryl group and the heterocyclic group may have, halogen atoms and alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio,
Acyl, acylamino, sulfonamide, carbamoyl, sulfamoyl, ureido, alkoxycarbonyl,
Examples include amine, sulfonyl, nitro, cyano, carboxyl and other groups.

Furthermore, R12 and Re may be formed by bonding with each other.
Examples of the membered ring and 6-membered ring include a chroman ring, and examples of the spiro ring include a spirobiine ring.

Further, examples of the 5-membered ring and 6-membered ring which may be formed by combining R8 and R9 or R9 and RIO with each other include an indane ring, a coumaran ring, a naphthalene ring, and a chroman ring, and examples of the spiro ring include a spirobiindane ring. , a subirobicumaran ring, a spirobiinman ring, etc.

These compounds are disclosed in U.S. Pat. No. 3,432,300, U.S. Pat.
, No. 700,455, No. 3.764,337, No. 3,
No. 935,016, No. 3,982,944, No. 4,2
No. 54,216, Special Publication No. 48-31625, No. 54-
No. 12337, JP-A-51-152225, JP-A No. 53-
No. 17729, No. 53-17729, No. 53-203
No. 27, No. 54-145530, No. 55-6321, No. 55-21004, British Patent No. 1,347,556
No., British Patent Publication No. 2,062,888, 2.066
．． No. 975, No. 2,077.455, etc.

Representative examples of compounds represented by the general formula [A-1[[1] are shown below, but the invention is not limited thereto.

Margin below ■-1 11-6 CH3 11-2 CH3 -7 11-3 1[-8 CH.

CR3 ff [-4 -9 C4Hs ■-5 CH3 ■-10 CH3 CJs (t) ■-15 H CH3 C4H9 (t) ■-22 H C6H1l (tl ■-16 H OCRCOOC2Hs I2825 ■-17 H H C) 13 ■-18 h CH3 ■-19 -24 ■-25 1 [-29 ■-30 ■-31 13c H3 ■-32 ■-33 3C H3 ■-42 H OCR2CH=C)12 ■-34 ■-35 -36 H3 ) 13C H3 3C H3 ■-43 OC82CH=CH2 ■-44 C・H17 (Sat) ■-45 SC12825 ■-46 CH3 The following margins are the general formula [A-I] of the present invention, - formula [A-I and - Compounds represented by the formula [A-II[' show good effects when at least two of them are used in combination, but preferred combinations include at least one of the compounds represented by the general formula [A-I].
species and at least one compound represented by the general formula [A-I[]; - at least one compound represented by the formula [A-] and a compound represented by the general formula [A-m]; At least one compound represented by the general formula [A-I[] and at least one compound represented by the general formula [A-III]; or - at least one compound represented by the formula [A-1] At least one compound represented by the general formula [A-n]; and at least one compound represented by the general formula [A-I] are used in combination.

The amount of the compound represented by the general formula [A-I] of the present invention, - formula [A-n] and - formula [A-I [[] (hereinafter referred to as the compound of the present invention) is determined according to the present invention. It is preferably 5 to 400 mol%, more preferably 1
It is 0 to 300 mol%.

The above compounds of the present invention can also be used in combination with other types of image stabilizers.

These compounds of the present invention are preferably present in the layer in which a magenta dye image is formed or in a layer adjacent thereto in the silver halide color photographic light-sensitive material.

Various methods are used as effective methods for incorporating the compound of the present invention into a silver halide color photographic light-sensitive material. A method similar to that described above can be used, and if necessary, the coupler can be dispersed and contained in the layer together with the coupler or separately.

The silver halide photographic light-sensitive material of the present invention may be one for monochrome use or one for multicolor use. In the case of a silver halide photosensitive material for multicolor use, magenta, yellow and cyan are usually used as photographic couplers. It has a structure in which a silver halide emulsion layer containing each coupler and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers, but the number and order of layers are determined by the important performance and purpose of use. It may be changed as appropriate.

The silver halide emulsion used in the silver halide photosensitive material of the present invention includes conventional halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any material used in silver oxide emulsions can be used.

The silver halide emulsion is chemically sensitized by conventional methods. Furthermore, it can be optically sensitized to a desired wavelength range.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, compounds known as antifoggants or stabilizers in the photographic industry may be added for the purpose of preventing fog during photographic processing and/or keeping photographic performance stable.

The silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation.

The silver halide color photographic material of the present invention may contain various other photographic additives. For example cJ
Antifoggants, development accelerators, gAM spreading agents, bleaching accelerators, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent whitening agents,
Color image fading prevention agent, antistatic agent, hardening agent, surfactant,
Plasticizers, wetting agents, etc. can be used. (research·
You can refer to Disclosure Magazine No. 17643. ) Furthermore, by coupling with a competing coupler and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, an antifogging agent, a chemical sensitizer, Compounds that release photographically useful fragments such as spectral sensitizers and desensitizers can be used.

The support for the silver halide color photographic light-sensitive material of the present invention is
Examples include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc., and a reflective layer may be used in combination.

These supports are appropriately selected depending on the intended use of the photosensitive material.

For coating the emulsion layer and other constituent layers used in the present invention, a number of coating methods can be used, such as dipping coating, air doctor coating, curtain coating, and hopper coating. Further, simultaneous coating of two or more layers by the methods described in US Pat. No. 2,781,791 and US Pat. No. 2,941,898 can also be used.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. It is preferable to do so.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and various layers such as a filter layer, anti-curling layer, protective layer, antihalation layer, etc. may be provided as constituent layers. They can be used in appropriate combinations. A hydrophilic colloid can be used as a binder in these constituent layers, and gelatin is preferably used.

Further, the various photographic additives mentioned in the explanation of the emulsion layer can be contained in the layer.

There are no particular restrictions on the method of processing a photographic light-sensitive material using the silver halide emulsion of the present invention, and any commonly known processing method can be applied. A method in which bleach-fixing is performed, followed by washing and/or stabilization treatment if necessary, or a method in which bleaching and fixing are carried out separately after color development, and further washing with water and/or stabilization treatment is carried out if necessary. However, the silver halide color photographic light-sensitive material of the present invention is suitable for rapid processing in the steps of color development, bleach-fixing, and washing (or stabilization).

[Example] Specific examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 A monochromatic color photographic material was prepared by sequentially applying the following layers to a paper support laminated on both sides with polyethylene from the support side to obtain Sample 1.

Layer 1: Emulsion layer Comparison below Cyan coupler (Ca) 0.48f/rr? ,
Silver chlorobromide emulsion (silver bromide content 70 mil%) converted to silver is 0.35 f/rr? , dibutyl phthalate 0.30
f/d and gelatin at 1.5. /rr? The coating was applied so that the coating amount was as follows.

Layer 2: Intermediate layer (ultraviolet absorber-containing layer) Ultraviolet absorber (UV-1) is added to 0.3. /rr? ', dibutyl phthalate 0.3t/rd, gelatin 1.2g
/rr? The coating was applied so that the coating amount was as follows.

Layer 3: Protective layer Gelatin was coated at a coating amount of 0.8 g/d.

In addition, 2,4-dichloro-6-hydroxy-5-triazine sodium was used as a hardening agent in layer 2, and gelatin 1 was added in layer 3.
It was added in an amount of 0.012 g/g.

The comparative cyan coupler (C-a) in the first layer was replaced with the cyan coupler shown in Table 1 in an equimolar amount as the comparative cyan coupler (C-a), and the compound of the present invention was added as shown in Table 1. Samples 2~
18 was created.

The amounts of the compounds of the present invention added in Table 1 are expressed in moles per mole of cyan coupler used.

Table 1 -a V-1 1 H -b 03H7(+) Each of the above photosensitive material samples 1 to 18 was exposed through an optical wedge and then processed in the following steps.

[Processing process (38℃) Color development gA 3 minutes 30 seconds bleach fixing
Wash with water for 1 minute and 30 seconds, dry for 1 minute
Drying: 60°C to 80°C for 2 minutes The composition of each treatment liquid is as follows.

[Color developer fi liquid] Pure water 800mJ Benzyl alcohol 15ml, 1l Hydroxylamine sulfate 2. OIr Potassium Bromide 1.0g Sodium Chloride
1.0 g potassium sulfite
2. Oftriethanolamine
2.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g 1-hydroxyethylindene-1°1-diphosphonic acid (60% aqueous solution) 1.5 mJl carbonic acid Potassium 32 gWh
tec 8B <50% water soluble i) 2mJ
(Fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to make 1J, 20% sodium hydroxide or 1
The pH was adjusted to 10.1 with 0% dilute sulfuric acid.

[Bleach-fix solution] Pure water 550m fJ Iron(I) ethylenediaminetetraacetate Ammonium salt 65.

Ammonium thiosulfate 85 g Sodium bisulfite 10 g Sodium metabisulfite 2 g Disodium ethylenediaminetetraacetate 20.

Add sodium bromide iog pure water to make IJ, and adjust to pH 7.0 with ammonia water or dilute sulfuric acid.
Adjust to.

Regarding Samples 1 to 18 treated above, ■ Spectral absorption maximum wavelength (
55Qnm when the reflection density at λmax) is 1.0
The reflection density (D,) was measured.

The smaller the value of D, the less asymmetric absorption in the green region and the better the color reproducibility.

In addition, the above treated sample was measured with a xenon fade meter.
While testing the light fastness of the cyan dye image by irradiating it for 1 day, each sample was exposed to a high temperature and high humidity atmosphere of 60°C and 80% RH for 1 day.
The cyan dye image was left to stand for 4 days, and the heat and humidity resistance of the cyan dye image was examined. The results obtained are shown in Table 2. However, the evaluation of the light fastness and heat/humidity resistance of the dye image is shown by the residual rate (expressed in percentage) of the dye after the double light and heat/humidity resistance tests with respect to the initial density of 1 and 0.

As shown in Table 2 below, the cyan coupler of the present invention has a small D and excellent color reproducibility, but when used alone, it has the disadvantage of extremely poor image storage stability. By using these compounds in combination, both light resistance and heat/humidity resistance are significantly improved, resulting in image storage stability that poses no practical problems.

Example 2 On a paper support laminated with polyethylene (titanium oxide content: 2.7 g/d), the following layers were sequentially coated from the support side to obtain a silver halide color photographic light-sensitive material (Sample 19).
-30) were prepared.

Layer 1 - 1.2g/rrf gelatin, 0.30g
/rd (in terms of silver, the same applies hereinafter) blue-sensitive silver chlorobromide emulsion (silver chloride content 99.3 mol - 6), 0.50 g/
0.80 g/rr dissolved in dioctyl phthalate of d
? A layer containing a yellow coupler (Ya).

Layer 2: Intermediate layer consisting of 0.7 g/d gelatin.

Layer 3...1.25g/rr11 gelatin, 0.22
g/rrr green-sensitive silver chlorobromide emulsion (silver chloride content 99.
0.62 g/rrr of magenta coupler (M
- a layer containing a).

Layer 4 - 1.2 g/rrf of gelatin and 1
2rw:/rr? An intermediate layer consisting of (AIC-1>).

Layer 5 = -1.4 g/d gelatin, 0.20 g/rr
f red-sensitive silver chlorobromide emulsion (silver chloride content 99.7 mol%
), 0.20 g/rr? A layer containing the cyan coupler shown in Table 3 (33.3 mol % based on silver halide) dissolved in dioctyl phthalate and the compound shown in Table 3 depending on the sample.

Layer 6...1.0 g/rrr gelatin and 0.2 g
0.3 g/n dissolved in /d dioctyl phthalate
A layer containing an ultraviolet absorber (UV-1).

Layer 7: A layer containing 0.5 g/rrf of gelatin.

In addition, as a hardening agent, 2.4-dichloro-6-hydroxy-3-) riazine sodium was added in layers 2.4 and 7.
Each was added in an amount of 0.017 g per 1 g of gelatin.

-a Cj -a 1 1 Margin below Each of the above photosensitive material samples 19 to 30 was exposed to light through an optical wedge and then processed in the following steps.

Processing temperature Time color development 34.7±0.3℃ 45 seconds bleach fixing
34.7±0.5℃ Stabilized for 45 seconds 30~34
Dry at 60-80°C for 60 seconds The composition of the treatment solution is as follows.

<Color developer> Pure water 800m I! Triethanolamine 8gN, N-diethylhydroxylamine 5g Potassium chloride
2g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g sodium tetrapolyphosphate 2g potassium carbonate
30g potassium sulfite
0.28 Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1 g Add pure water to bring the total volume to 11, and adjust the pH to 10.2.

Bleach type S solution〉 Pure water 800m R Ethylenediaminetetraacetate iron (II
Water salt 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100mn ammonium sulfite (40% solution)
27.5m 12 Add water to make the total volume II2,
Adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing liquid> Pure water 800m n5
-Chloro-2-methyl-4-isothiazolin-3-one 1g 1-hydroxyethylidene-1,1-diphosphonic acid 2g Add water to make 11, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

Samples 19 to 30 were tested in the same manner as in Example 1 to examine the durability of cyan dye images.

The results are shown in Table 4.

The amount of the compound of the present invention added is shown in the number of moles per mole of cyan coupler.

From this result, when the cyan coupler according to the present invention is used alone, the light resistance and heat and humidity resistance are extremely poor, but when the compound according to the present invention is used in combination for 2 seconds or more, the cyan coupler according to the present invention is extremely effective in stabilizing the dye image. I understand that there is something.

Furthermore, the samples of the present invention showed extremely little discoloration or fading of the cyan dye, and as a whole color photographic light-sensitive material after both light tests, the color balance with the yellow and magenta couplers was good, and the color reproducibility remained extremely good. was.

Example 3 On the surface of a 135 μm thick paper support whose front surface was coated with polyethylene containing titanium oxide and whose back surface was coated with polyethylene, the first to seventh layers shown below were coated on the back surface. The layers were coated to create a color photosensitive material.

In the table, the amount added is shown in z/'cd, provided that the silver halide emulsion is expressed in terms of silver.

7th layer (protective layer) Addition amount Gelatin 1.0 Silicon dioxide powder (average particle size 3 μm) 0.03 6th layer (ultraviolet absorption layer) Gelatin 0.6 Ultraviolet absorber (UV-1) 0.2 Ultraviolet absorption Agent (
UV-2> Anti-color mixture agent (HQ-1) NP vP Anti-irradiation dye (AI-2 5th red-sensitive layer) Red-sensitive halogenated spectrally sensitized with Seratin sensitizing dye (D-3) Silver emulsion cyan coupler (C-a) Anti-stinting agent (HQ-1) B-1 4th layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-1> Ultraviolet absorber (tJV-2) Color mixing inhibitor (HQ -1> NP 3rd layer (green sensitive layer) Gelatin 0.2 0.01 0.2 0.03 ) 0.065 1.40 0.24 0.40 0.01 0.30 1.30 0.40 0.40 0.03 0.40 1.40 Green-sensitive silver halide emulsion spectrally sensitized with sensitizing dye (D-2>) 0.27 Magenta coupler (M-b) 0.35 Yellow coupler (Y- c) 0.12 dye image stabilizer (
ST-3) 0.20 dye image stabilizer (ST
-4) 0.10 stain inhibitor (HQ-1)
0.01HB-20JO Irradiation prevention dye (AI-1) 0.01 2nd layer (intermediate layer) Gelatin 1.20 Color mixing inhibitor (HQ-1) 0.12 DIDP 0.15 1st layer (blue feeling Layer) Gelatin 1.30 Blue-sensitive silver halide emulsion spectrally sensitized with sensitizing dye (D-1) 0.30 Yellow coupler (y-b) 0.80 Dye image stabilizer (ST-1) 0 .30 dye image stabilizer (S
T-2) 0.20 stain inhibitor (HQ-1
) 0.028 B-20,20 Anti-irradiation dye (AI-3>0.06
3 Back layer (protective layer) Gelatin 3.00 Surfactant (S-2) 0.01 Hardener
(H-1) 0.07 Silica ((average particle size 5 μm) 0.3 Surfactants (S-i>, (S-2>) as coating aids on the emulsion layer side and (H -1) and (H-2) were used.

Based on the above configuration, samples 31 to 40 were prepared by changing the cyan coupler in the fifth layer as shown in Table 5 and adding the compound of the present invention.

Margin below -b -c 1 ST-3 ST-4 ST-1 V-2 H 1 CJs(t) CsH+ + (ti DOP Nijiokuti L. phthalate P Two of Nilf Ta Leh to IDP diisodecyl phthalate 　V　P :Poly vinyl pyrrolidone B-1 B-2 0=P(C@H+7h Q I I I-1 (CH2) 3SO3 C2) I5 -1 C2H.

CH2C00CHaCHC4Hs CHCOOCH2CHC4H@ 03Na 2H5 -2 CH2COOCH2(CFaCFzl eHCHCOO
CHa (CF2CF212H03Na 1 C(CH2SO2CH-CH2: a I-2 I-3 -2 2H5 (CH2+ 2'sυ3 1UH2125Uzllllllll; 1rlslz Table (1) Sample N.

The amount of cyan coupler added in samples No. 32 to 39 is as follows:
The same molar amount as cyan coupler Ca of No. 31 was added.

(2) [A engineering], [A-n], [A-I[[The amount of addition is It is expressed as the number of moles per mole of cyan coupler.

The above sample has 175@ dots per inch and the dot area is 0%.
A black and white transmission negative varying from 100% to 100% was exposed in vacuum.

The light source during exposure is a fluorescent lamp, and the color separation filters are Kotatsukratten filters for blue, green, and red.
47 B, NQ 61 and NQ 29 were used.

Next, processing was performed according to the following processing steps.

Processing process temperature Color development 39.8℃ Bleach fixing 33℃ Stabilization 33℃ Dry 70℃ The composition of each treatment liquid is as follows.

Color developer > Hydroxylamine sulfate Potassium carbonate Sodium chloride Sodium bromide Sodium sulfite anhydrous Time 2 minutes 45 seconds 3 minutes 1 minute 2.0g 25.0g o, 1g o, 2g 2, Og Benzyl alcohol 10.0m Ju
1N-Ethyl-N-β-hydroxylethyl 4-aminoaniline sulfate Add 4.5g of water and add
J2 and adjusted to pH 10.15 using sodium hydroxide.

Bleach-fix solution> Ethylenediaminetetraacetate iron <1) Sodium salt 60g Ammonium thiosulfate 100g Sodium bisulfite 20g Water was added to make II2, and the pH was adjusted to 7.0 using sulfuric acid.

Stabilizing liquid> 5-chloro-2-methyl-4=isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0° ethylenediaminetetraacetic acid 1.0 g hydroxide ammonium (70% water soluble 3.0) ammonium sulfite 3.0g fluorescent brightener (4.4
'-Diaminostilbendisulfonic acid derivative #) 1. Add Sr water to bring the pH to 11, and adjust the pH to 7 with sulfuric acid or potassium hydroxide.
．． Key M to 0.

The color tone of the cyan coloring dye of the obtained treated sample was evaluated by the method shown below.

The results are shown in Table 6.

Margin cyan color tone evaluation The color tone of the cyan monochromatic portion of the finished halftone image was visually compared with a printed ink color sample, and the color tone was evaluated using the following grades.

Grade Color Tolerance Level Close to printing ink.
The light resistance of the cyan dye image was examined by irradiating it for 24 hours.

The results obtained are shown in Table 6.

Table 6 In the silver halide color photographic light-sensitive material of the present invention,
It is possible to form a clear cyan dye image with excellent spectral absorption characteristics, and in color proofing, it is possible to obtain color tone reproduction similar to that of printing ink.

Furthermore, a cyan image that is stable against light, heat, and humidity can be obtained.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one cyan coupler represented by the following general formula [C-I], and the following: General formula [A-I], general formula [A-II]
and a silver halide color photographic light-sensitive material containing at least two compounds represented by the general formula [A-III]. General formula [C-I] ▲ Numerical formulas, chemical formulas, tables, etc. represent. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. ] General formula [A-I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_3 and R_4 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. R_5 and R_6 are each a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acylamino group, a sulfonyl group, a sulfonamide group, or a hydroxy group. represents. m and n each represent an integer of 0 to 4, and m is 2 to
When an integer of 4, each R_5 may be the same or different. Moreover, when n is an integer of 2 to 4, each R_6 may be the same or different. A represents a divalent linking group. ] General formula [A-II] ▲ Numerical formulas, chemical formulas, tables, etc. Represents the necessary nonmetallic atomic group. ] General formula [A-III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1_3 is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a hetero group, or ▲
There are mathematical formulas, chemical formulas, tables, etc. Represents ▼. Here R_1
_3', R_1_3'' and R_1_3'' may be the same or different, and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group or an aryloxy group. R_8, R_9, R_1_0, R_1_1 and R_1_
2 may be the same or different, and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an acylamino group, a sulfonamido group, an alkylamino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, and an aryloxy group. Represents a carbonyl group, a halogen atom, or -O-R_1_4. Here R_1_4
represents the same group as R_1_3. Also, R_
1_3 and R_8 may be combined with each other to form a 5-membered ring, a 6-membered ring, or a spiro ring, and R_8 and R_9 or R_9
and R_1_0 may be combined with each other to form a 5-membered ring, a 6-membered ring, or a spiro ring. ]