JPS62178962A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To stabilize a dye image to light by incorporating >=1 specific cyan couplers and >=1 specific compds. into the titled material. CONSTITUTION:This material contains at least one of the cyan coupler expressed by formula I and at least one of the compd. expressed by formula II. In formula I, R1, R2 respectively denote a hydrogen atom, alkyl group, etc., R3 denotes an aryloxy group, etc., or heterocyclic group. In formula II, R4, R5 respectively denote a hydrogen atom, alkyl group, etc., R7 denotes an alkyl group, etc., R6 denotes a substituent, l denotes an integer 0 or 1-4. the coupler is usually used in a silver halide emulsion layer, more particularly a red sensitive emulsion layer. The amt. of the coupler to be added is in a 2X10<-3>-8X10<-1>mol, more preferably 1X10<-2>-5X10<-1>mol range per mol of the silver halide. The compd. expressed by formula II is added into the photosensitive material in order to maintain the fastness to light of the cyan dye image after a developing process for a long period of time and is, therefore, preferably the compd. which does not flow out or hydrolyze during the developing process.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material, and in detail,
This invention relates to a silver halide color photographic light-sensitive material in which a dye image is stable against light and the occurrence of staining is prevented.

[Background of the invention]

Conventionally, when a silver halide color photographic light-sensitive material is imagewise exposed and color developed, an oxidized product of an aromatic primary amine color developing agent and a color former undergo a coupling reaction, resulting in the formation of, for example, indophenol, indophenol, and indophenol. It is well known that aniline, ingmin, azomethine, 7-e/xazine, 7-enazine, and all of these pigments are produced and color images are formed. In such photographic systems, a subtractive color reproduction method is usually adopted, and a color forming agent having an additional color relationship, that is, yellow (2) A silver lodenide color photographic light-sensitive material containing a coupler that develops magenta and cyan colors is used.

Examples of couplers used to form the above-mentioned yellow image include acylacetanilide couplers, and examples of couplers used to form magenta images include pyrazolone, virazolobenzimiguzole, pyrazolotriazole, and indacylon couplers. Couplers are known, and as couplers for forming cyan images, for example, phenol or 7-tole couplers are generally used.

It is desired that the dye image obtained in this way does not change color or fade even if it is exposed to light for a long time or stored under high temperature and high humidity.

Therefore, many attempts have been made to improve the stability of dye images, and only a few techniques have been put into practical use.

For example, U.S. Patent No. 3,432,300 describes 6-hydroxychroman compounds, and U.S. Pat.
Hydroxycoumaran compound, Japanese Patent Publication No. 47-47245
No. 49-20977 contains amine-based compounds, No. 49-20977 contains non-hydroxy-bilobychroman-based compounds, and JP-A-48-2
No. 6133 includes bis-7-7-ol compounds, No. 50-63
No. 39 is a 1,000-obis 7-technol-based compound,
No. 32785 contains hydroxyin bean-based compounds, JP-A No. 54-48538 contains hydroquinone diether compounds, JP-A No. 55-124141 contains hydroquinone monoether compounds, and JP-A No. 56-159644 contains noalkoxysbilovingone compounds. Compounds and the like are disclosed as dye image stabilizers.

Also, JP-A Nos. 50-87649, 54-62826, 54-62827, 54-65185, 5
No. 4-69580, No. 54-72780, No. 54-8
No. 2234, No. 54-82384, No. 54-8238
No. 5, No. 54-82386, No. 54-136581, No. 54-136582, No. 55-12129, No. 55-152750, No. 56-59219 - Inter-bow R
-CIA 111 minutes- 6-16711 koma 6-
No. 168652, No. 57-161744, No. 58-1
No. 29429 and others similarly describe metal chelate compounds as dye image stabilizers.

Normally, in silver halide color photographic materials (hereinafter referred to as color photographic materials), magenta dye images have significantly lower stability against light than other yellow and cyan dye images, so the above-mentioned various dye image stabilization methods are required. The agent is also primarily intended for stabilizing magenta dye images. Color photographic image stabilization technology has advanced dramatically in recent years, as these dye image stabilizers do significantly improve the light stability of magenta dye images.

Cyan dye images have the second lowest stability against light after magenta dye images, and once the stability of magenta dye images has been significantly improved, it is natural that technology to improve the stability of cyan dye images will be required. .

However, the above dye image stabilizers hardly contribute to the stabilization of cyan dye images, and a new type of cyan dye image stabilization technology is strongly desired.

[Purpose of the invention]

The present invention has been made in view of the above problems, and an object of the present invention is to provide a color photographic material in which the light fastness of cyan dye images is significantly improved.

[Structure of the invention]

The above object of the present invention is achieved by a silver halide photographic material containing at least one cyan coupler represented by the following general formula [Natsu] and at least one compound represented by the following general formula [■] be done.

General formula (1) In the formula, R1 and R2 are each a hydrogen atom, an alkyl group,
Represents a cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, acylamide group, carbamoyl group, sulfonamide group, sulfamoyl group or ureido group. R1 represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, or a heterocyclic group. Mar:
R2 and R1 may be bonded to each other to form a 5-shell or 6-shell ring.

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

General formula [11] [In the formula, R9 and R5 each represent a hydrogen atom, a furkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R7 represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. represents a group or a heterocyclic group. R6 represents a substituent, and p represents 0 or an integer of 1-4.

OS OR8SRs R3 R1 and R each represent a hydrogen atom or an alkyl group, and may be the same or different. Further, R1 and R5 may be combined to form a 5-shell or 6-shell ring.@When p is 2 or more, a plurality of R6's may be the same or different. Furthermore R6
may form a 5-shell or 6-shell ring together with R1 and V/or R9, and R4 and the nitrogen atom adjacent to R1.

] [Specific structure of the invention] Next, the present invention will be specifically explained.

In the cyan coupler represented by the general formula [I] according to the present invention, the alkyl group represented by R3 or R2 has 1 to 32 carbon atoms, and the alkenyl group has 2 to 32 carbon atoms. The cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms;
Alkenyl groups may be linear or branched.

In addition, these alkyl groups, alkenyl groups, and cycloalkyl groups include substituents [e.g., aryl and Schiff), halogen atoms, heterocycles, alkyl, alkenyl, and cycloalkyl groups, as well as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl groups. Those substituted through a carbonyl group such as, and those substituted through a hetero atom (specifically, those substituted through an oxygen atom such as hytomoxy, flukoxy, aryloxy, heterocyclic oxy, acyloxy, carbamoyloxy, etc.) What to do, nitro,
7mino (including nofurkylami 7, etc.), sul7amoylamino, alfkidicarbonylamino, aryloxycarbonylamino/, acylami/, sulfonamide, imide, ureido, etc. substituted via nitrogen atom, alkylthio, arylthio, hetero ring thio, sulfonyl,
sulfinyl, sulfamoyl, etc., which are substituted via a sulfur atom, and phosphonyl, which is substituted via a phosphorus atom, etc.).

Specifically, for example, methyl group, ethyl group, isopropyl group, butyl group, pentadecyl group, hebutadecyl group, 1
-hexyl/nyl group, 1,1'-dipentyl/nyl group,
2-chloro-t-1+ group, trifluoromethyl group, 1
-ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-not-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-l-butanesulfonami/phenoxypropyl group, 3-4'lα-[4"(p-hydroxybenzenesulfonyl)phenoxyfudodecanoylami/) phenylpropyl group, 3-+4'-(α-(2", 4"-
no[-7mil7eth/xy)butanamido]phenyl)
-propyl group, 4-[α-(0-chlorophenoxy)tetradecanamidophenoxy]propyl group, allyl group,
Examples include propenyl group, decenyl group, cyclopentyl group, and cycloalkyl group.

The alkoxy group represented by R1 or R2 may be further substituted with the substituents listed above for the alkyl group, such as methoxy group, propoxy group, 2-ethoxyethoxy group, pentadecyloxy group, -dodecyloxyethoxy group, 7enethyloxyethoxy group, etc.

The aryloxy group represented by R1 or R2 is preferably a phenyloxy group, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group, for example, 7ethyloxy group, pt-butyl 7
Examples include enoxy group and m-pentadecylphenoxy group.

The acylami 7 groups represented by R1 or R2 include alkylcarbonyl amine 7 groups, arylcarbonyl amine 7 groups,
groups (preferably phenylcarbonylamide 7 groups), etc., which may further have a substituent, specifically an acetamide group, an α-ethylpropanamide group, an N-phenylacetamide group, a dodecanamide group, 2, 4-di-t-amyl 7ethoxyacetamide group, α-3-t-butyl 4-
Examples include hydroxyphenoxybutanamide group.

The carbamoyl group represented by R1 or R2 may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-methylcarbamoyl group, N,N
-dibutylcarbamoyl group, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-13-(2,4-no-L-7
Examples include milphenoxy)propyl)carbamoyl group and the like. - Examples of the sulfonamide group represented by R3 or R2 include an alkylsulfonylamino group and an arylsulfonylamino group, and may further have a substituent. Specifically, 7 methylsulfonylamino groups, a pentadecylsulfonylamino group, a benzenesulfonamide group, p-
Toluenesulfonamide group, 2-methoxy-5-t-7
Examples include milbenzenesulfonamide group.

The sulfamoyl group represented by R1 or R2 may be substituted with a furkyl group, an aryl group (preferably a phenyl group), etc., such as an N-propylsulfamoyl group, an N-propylsulfamoyl group,
, N-noethylsul7amoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N
-dodecylsulfamoyl group, N-phenylsulfamoyl group and the like.

The ureido group represented by R1 or R2 is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group, an N-methyl-N-decylureido group, an N-phenylureido group,
Examples include N-p-tolylureido H1N-p-ethylsulfonylureido group.

As the alkyl group, cycloalkyl group, alkenyl group, alkoxy group or aryloxy group represented by R1, the same groups as those explained for R1 and R2''C can be mentioned.

Examples of the halogen atom represented by R3 include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred.

The aryl group represented by R3 is preferably a phenyl group, and may have a substituent (for example, an alkyl group, an alkoxy group, a 7-sylami7 group, etc.)1.111 Specifically, phenyl groups, 4 -t-7thyl heptanyl group,
2,4-not-7 milphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-t-butyl7eth-7xy)tetradecanamidophenyl group and the like.

The heterocyclic group represented by R1 is preferably a 5- to 7-shell heterocyclic group, which may be substituted or fused.

Specific examples include 2-furyl group, 2-chenyl group, 2-biriminonyl group, and 2-benzothiazolyl group.

R2 and R7 may be bonded to each other to form a 5- to 6-shell ring, and include, for example, cyan couplers represented by the following general formulas (I[I), [■], and (V).

General formula (III) Here, R, and X have the same meanings as R and X in general formula [I].

General formula [■] Here, R, and X have the same meanings as R, and X in general formula CI], and R1° or R11 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, Represents an alkylthio group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, or a sia/group.

General formula (V) where R,,X are R,,X in general formula [■], and R
1□ Each has the same meaning, Z represents 10-1-Y- or ■ R32 -8-, R1□ and R13 represent the general formula [IV]
represents the same group as the group listed for Rlo or RI+.

RI4 represents a hydrogen atom, an alkyl group, or an aryl group.

In the present invention, cyan couplers represented by the following general formulas (Vl) and [■] are preferable. 1゜General formula (Vl) 0■ Here, R15 is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a hetero Represents a ring group.

R16 represents an alkyl group, and R17 represents a hydrogen atom or a halogen atom. X has the same meaning as X in general formula (1).

General formula [■] Here, R15, R17 and X have the same meanings as R l 5 , R+ 7 and X in the general formula (V[], respectively, and RIS represents a group having the same meaning as RI5.

Furthermore, in general formula (VI), R15 is an alkyl group, R06 is a lower furkyl group having 1 to 4 carbon atoms, and R+
In the general formula [■], the coupler in which 7 represents a chlorine atom is most preferably a coupler group in which R7, R17, and R17 each represent an alkyl group or an aryl group.

In general formulas (1) to [■], the campling leaving group represented by
fluorine atom, etc.), alkoxy groups (e.g., nidoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxymethoxy group, ethylsulfonylethoxy group, etc.), aryloxy groups (e.g., 7ethyloxy group, naphthyloxy group, etc.) ), acyloxy groups (e.g. ace1
xy group, tetrazocaphyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), acylami 7 group (e.g., nochloroacetyl amine 7 group, heptafluorobutylene group), 7 groups of rylamide, etc.), 7 groups of sulfonyl amine (
(e.g., 7 methanesulfonylamide groups, 7 toluenesulfonyloxy groups, etc.), alkoxycarbonyloxy groups (e.g., ethoxycarbonyloxy groups, benoloxycarbonyloxy groups, etc.), aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy groups) and imide groups (eg, succinimide group, hydantoinyl group, etc.).

Furthermore, in the general formula CI[[]~[■], RI O~
Specific examples of the halogen atom, alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group each represented by RIB include the same groups as those listed for R3, R2 or R1 in general formula [■]. be able to.

Typical specific examples of the cyan coupler represented by the general formula [1] are shown below, but the present invention is not limited thereto.

Below margin ^-2 ^-6 ^-8 ^-9 0■ ^-16 0M Δ-18 -1Q ^-20 ^-21 H ^-22 ^-23 I ^-24 ^-25 nll 4H9 ^-36 ^-37 ^-38 ^-39 ^-40 8-42 Shil 8-43 ^-44 8-45 ^-46 ^-48 ^-49 ^-50 Δ-51 8-52 ^-53 ^-56 ＾-58 ＾-59 Δ-60 2H5 ＾-65 Δ-67 +Ill ＾-68 0■ ＾-69 ＾-Flow Patent No. 2,423,730, Patent No. 2,801.171
No. 49-11572, Japanese Patent Publication No. 1120-1972
No. 38, No. 50-134644, No. 53-10963
No. 0, No. 54-55380, No. 56-65134,
No. 56-80045, No. 56-104333, No. 5
No. 7-155538, No. 57-204543, No. 57
-204545, 58-98731, 58-1
No. 05229, No. 59-31953, No. 59-319
No. 54, No. 59-61834, No. 59-69755, No. 59-74556, No. 59-97143, No. 5
No. 9-111645, No. 59-146050, No. 59
-166956, 60-159851, etc., and can be synthesized according to the methods described.

The coupler of the present invention is usually used in a silver halide emulsion layer, especially a red-sensitive emulsion layer, and the amount added is 2 x 10-co to 8X 10-' mol per mol of silver halide, preferably lX
It ranges from 10-2 to 5X 10-' moles.

Next, the dye image stabilizer represented by the general formula (If) used in combination with the coupler represented by the general formula [■] in the present invention will be explained.

General formula (I[) Specific examples of the alkyl group, cycloalkyl group, and alkenyl group represented by %R4, R5, or R7 in general formula (II) include R3 and R in general formula [1] above.
The groups mentioned in 2 can be mentioned.

Specific examples of the aryl group and heterocyclic group represented by R9 or R1 include the groups described for R3 in general formula CI).

The same applies to the alkyl group represented by R8 or R1 when 0 Rs S Rs Rs.

R6 is a substituent that can be substituted on the benzene ring and is not particularly limited, but specifically includes a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, Acyloxy group, acylamide 7 group, amino group, sulfonamide group, carbamoyl group, sulfonamide group,
Examples include an alkoxycarbonyl group and an aryloxycarbonyl group.

Specific examples of the halogen atom, alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, acylamino group, sulfonamide group, carbamoyl group, and sulfonyl group represented by R6 include R of the general formula CI) ，
, R2 or R1.

Examples of the alkenoxy group represented by R6 include a propenyloxy group and a hexenyloxy group, and these groups may further have a substituent.

The alkylthio group represented by R6 may further have a substituent, for example, an ethylthio group, a dodecylthio group,
Examples include octadecylthio group, 7enethylthio group, and 3-727xyprobylthio group.

The arylthio group represented by R6 is phenylthio group at
&? ; Examples include p-7cetamino7enylthio group.

Examples of the acyl group represented by R5 include acetyl group,
Phenylacetyl group, dodeca/yl group, ff-214-
Examples include a furkylcarbonyl group such as a di-t-amylphenoxybutanoyl group, a 7-aryl carbonyl group such as a benzoyl group, a 3-bentadecylolisipenzoyl group, and a p-chlorobenzoyl group.

The acyloxy group represented by R6 includes, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-chloroacetyloxy group, etc. , benzoyloxy group, etc.

The ami7 group represented by R6 may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as ethylamino group, anilino group, m-chloroanily7 group, 3-pentadecyloxyluponylanily7 group, 2-
Examples include 7 chloro-5-hexadecaneamide aniline groups.

The alkoxycarbonyl group represented by R6 may further have a substituent, such as a methoxycarbonyl group, a methoxyethoxycarbonyl group, an octadecyloxycarbonyl group, and the like.

As the aryloxycarbonyl group represented by R6,
It may be further substituted, and examples thereof include a 7-ethyloxycarbonyl group and a 4-methylphenoxycarbonyl group.

Further, each of the above-mentioned R, RS, and R7 groups includes those having a substituent. Examples of the substituent include a hydroxy group, an alkoxy group, an aryl group, an acylamide group, a sulfonamide group, an aryloxy group, a carbamoyl group, a sulfonyl group, a sulfonyl group, a vinylsulfonyl group, a nitro group, a cyano group, and a halogen atom. , a carboxyl group, an amide group, an alkylamino group, an alkoxycarbonyl group, an acyl group, an arylaminocarbonyloxy group, an acyloxy group, or a heterocyclic group.

Further, in the aryl group, for example, two adjacent groups may cooperate to form a methylenezoxy ring.

Next, typical examples of the compound represented by the general formula (II) will be shown, but the present invention is not limited thereto.

Typical synthesis examples of the compound represented by the general formula (II) used in the present invention are shown below.

Synthesis Example 1 (Synthesis of Exemplified Compound B-5) 1 g of N-(4-phenyloxycarbonylamino-2,5-dibutoxyphenyl)morpholine, N-(4-amino-2°5-dibutoxyphenyl)morpholine hydrochloric acid [0.811F and 0.172 of imidazole are mixed with 5011 of toluene and reacted under heating under reflux for 3 hours. After reaction, 100ml
of water was added, extracted with ethyl acetate, washed twice with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting purple-white solid was treated with activated carbon and then recrystallized from methanol to obtain 0.7 g of white crystals. Melting point 175-17
6°CFD mass spectrum (670), NMR are both N
.

The structure of N'-bis(4-morpholino-2,5-dibutoxyphenyl)urea was supported.

Elemental analysis value (CpJssNn07) Theoretical value (%) C: 66.24 ■: 8.71
N: 8.35 Actual value (%) C: 66.18 11:
8.73 N: 8.40 Synthesis Example 2 (Exemplary Compound B-
Synthesis of 11) N-(4-ami/-2,5-dibutoxyphenyl)morpholine hydrochloride 1 g and sodium hydrogen carbonate 0
．． 259 with n-butanol-water (2:1) mixed solvent 45
11. The mixture was heated to 95° C. under a nitrogen stream, and 0.77 g of butyl bromide was added dropwise thereto, followed by further reaction for 6 hours with stirring. After the reaction, the mixture is extracted with 2011 ethyl acetate, washed twice with water, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the residue was purified by column chromatography to give 0.2. A pale yellow oil was obtained. According to the FD mass spectrum (37B) and NMR, the above compound is N-(4
It was confirmed that it was -butylamino-2<5-dibutoxyphenyl)morpholine.

Elemental analysis value (Cz2H*@N20) Theoretical value (%) C:69.80 11:10.11
N near, 43 actual value (%) C: 69.77 +
1:10,22 Nia, 40 Synthesis Example 3 (Synthesis of Exemplary Compound B-12) 3.58 g of N-(4-7minor 2,5-dibutoxyphenyl)morpholine hydrochloride and pyrinone L, 6 ml were added to benzene 6011 Mix with. 0.71.
After adding ethyl incyanate dropwise at room temperature with stirring,
Allow to react for an additional hour. After adding 60 ml of ethyl acetate to the reaction solution, it is poured into water to extract the ethyl acetate layer, washed twice with water, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the deep purple residue was decolorized by treatment with activated carbon, and then recrystallized from methanol to obtain Ni4-(3-ethylureido)-2,
White crystals of 5-dibutoxyphenyl)morpholine 1.5
I got g. Melting point 125-127℃ FD mass spectrum (
393) and NMR both supported the above structure.

Elemental analysis value (C2, tl-sNao-) theoretical value (%)
C: 64.09 1+: 8.96 N: 10.68
Actual value (%) C: 64.21 H: 8,96
N: 10.68 Synthesis Example 4 (Synthesis of Exemplified Compound B-15) Hydroquinone 22. , 60 g of aniline and 0.4 g of triethylphos-7a) in an autoclave, 30
The mixture was heated to 0° C. and reacted for 4.5 hours while stirring. The reaction mixture was distilled under reduced pressure at 220-225°C to obtain a fraction 39. I got it.

FD mass spectrum (260), N, N'- from NHR
It was confirmed to be diphenyl-p-phenylenediamine.

Elemental analysis value (C,, H,, N2) Theoretical value (%) C: 83.05 H: 6.19
N: 1G, 76 actual value (%) C: 82.97 11
:6.21 N:10.70 Synthesis Example 5 (Exemplary Compound
Synthesis of B-17) N-(4-7minor 2,5-dibutoxyphenyl)morpholine hydrochloride 139 and pyrinone 9zt
) is mixed with ethyl acetate 150a+1. α-2,4-
Not t-amylphenoxybutanoic acid chloride 12.2g
was added under stirring at room temperature and allowed to react for an additional hour. Pour the reaction mixture into water, add 300z1 of ethyl acetate and extract.
After washing twice with water, dry with anhydrous sodium sulfate. Ethyl acetate was distilled off under reduced pressure, the dark purple residue was treated with activated carbon, and then recrystallized from ethyl acetate to give N-(2,5-dibutoxy-4
-(α-2,4-p-t-7milphenoxy)butanamidophenyl)morpholine white crystals 6FI were obtained.

Melting point 114-115°C FD mass spectrum (624),
Both NHR supported the above structure.

Elemental analysis value (C38H6°N20s) Theoretical value (%) C near 3,03 11:9.68
N: 4.48 Actual sinus value (%) C near 3. OOI+:9
．． 70 N: 4.48 The amount of the compound represented by the general formula [II] of the present invention used is preferably 5 to 300 mol% relative to the coupler represented by the general formula [I] of the present invention,
More preferably, it is 10 to 200 mol%.

The compound represented by the general formula [I[) of the present invention is added to the light-sensitive material in order to maintain the light fastness of the cyan dye image over a long period of time after processing. Therefore, the compound may be washed out or undergo changes (e.g. hydrolysis) during the development process.
Preferably one that does not. To this end, in general formula (n), the total number of carbon atoms of the substituents represented by R4, R5, R6 and R7 is preferably 10 or more, most preferably 13 or more. Compounds that satisfy this condition have extremely low leakage from the photosensitive material into the processing solution during development processing, are more oil-soluble, are less susceptible to the effects of aqueous processing solutions, and, for example, have good resistance to hydrolysis. increasing,
more effective.

In the silver halide photographic light-sensitive material of the present invention, other dye image stabilizers may be added to the cyan dye image stabilizer of the present invention, such as U.S. Pat.
, 982,944, 4,254,216, JP 55-21004, JP 54-145530, GB 2,077.455, GB 2,062.888, U.S. Pat. No. 764,337, 3,432°30
No. 0, No. 3,574,627, No. 3,573,050
No., JP-A-52-152225, JP-A No. 53-20327
No. 53-17729, No. 55-6321, No. 5
No. 4-48538, No. 56-$59644, No. 59-
No. 87456, British Patent No. 1,347,556, Publication No. 2,066.975, Japanese Patent Publication No. 12337/1982, Japanese Patent Publication No. 48-31625, U.S. Patent No. 3,700,455, etc. A compound or a phenyl ether compound can also be used in combination. Also, JP-A-59
Hinguntoamine compounds described in No. 53846 and No. 59-78344 can also be used in combination.

It is preferable that the cyan coupler of the present invention and the compound represented by the general formula (l[) of the present invention are used in the same layer,
The compound may be used in a layer adjacent to the layer in which the coupler is present.

The silver halide photographic light-sensitive material of the present invention can be applied to, for example, color black and white films, and color photographic paper, but the present invention is particularly suitable when applied to color photographic paper used for direct viewing. The effects of this will be effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, may be for monochrome use or for multicolor use. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-photosensitive silver halide emulsion layer are usually used. The appropriate number and order of the layers on the support! Although it has a structure of IIt layers, the number of calendars and the order of the layers may be changed as appropriate depending on the important performance and purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes (a) conventional silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride; Any of those used in silver halide emulsions can be used.

The silver halide grains used in the silver halide emulsion may be obtained by any one of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, considering the critical growth rate of silver denride crystals, growth may be performed by adding /% ride ions and silver ions sequentially or simultaneously while controlling the pH + pAg in the mixing pot. The silver halide composition of the grains may be changed using the convergence run method. Particle size, particle shape, particle size distribution, and particle length velocity can be controlled.

The silver halide grains used in silver halide emulsions are formed with cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. during the grain formation and/or growth process. Metal ions can be added to the inside of the particles and/or on the surface of the particles using complex salts, and reduction-sensitized nuclei can be created inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can be granted.

The silver halide emulsion may be freed of unnecessary soluble salts after the growth of silver halide grains is completed, or may be left in the silver halide emulsion. It can be carried out based on the method described.

Silver lodenide grains used in silver halide emulsions are:
The inside and the surface may be composed of uniform layers or may be composed of different layers.

The /% silver halide grains used in silver halide emulsions are:
It may be a particle in which a latent image is mainly formed on the surface, or it may be a particle in which a latent image is mainly formed inside the particle.

The silver halide grains used in the silver halide emulsion may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of (1001 planes to (1111 planes) can be used. Also, particles having a composite model number of these crystal forms may be used, or particles of various crystal forms may be mixed.

The silver halide emulsion may be a mixture of two or more silver halide emulsions formed separately.

The silver halide emulsion is chemically sensitized by conventional methods. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensing methods and the like can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dye may be used alone or in combination of two or more, and together with the sensitizing dye, it may be a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light. In addition, a supersensitizer that enhances the sensitizing action of the sensitizing dye may be included in the emulsion.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, silver halide emulsions may be added during chemical ripening, and/or at the end of chemical ripening, and/or after chemical ripening, for the purpose of preventing fog during photographic processing and/or keeping photographic performance stable. Compounds known in the photographic industry as antifoggants or stabilizers can be added prior to coating.

As a binder (or protective colloid) for silver halide emulsions, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention can be hardened by binding binder (or protective colloid) molecules and using a hardening agent alone or in combination to increase the film strength. be done. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic material of the present invention.

The photographic agent layer and other hydrophilic colloid layers of the silver halide photographic material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. I can do it.

In the emulsion layer of the silver halide photographic light-sensitive material of the present invention, aromatic primary amine development compounds such as 11 (for example, I)-phenylenenoamine derivatives, amino 7
A dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized form of (--ol derivatives, etc.). The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler for the blue light-sensitive emulsion layer. However, the magenta dye-forming coupler according to the present invention is used in the green light-sensitive emulsion layer, and the cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, color photographic materials may be created using different combinations from the above (1).

Yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilide M); magenta dye-forming couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole, l1i
ffi acylacetonitrile couplers and the like, and cyan dye-forming couplers include the 7 toll coupler and the V7 e/-coubrar represented by the general formula [I] of the present invention.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. It may be either 2-equivalent.

Hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface can be processed using various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. The oil-in-water emulsion dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives such as couplers, and is usually mixed with a high boiling point organic solvent having a boiling point of about 150°C or higher, and if necessary, a low boiling point and/or a high boiling point organic solvent. Alternatively, dissolve it in combination with a water-soluble organic solvent, and emulsify it by using a surfactant in a hydrophilic binder such as an aqueous gelatin solution and using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. After being dispersed, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent at the same time as the dispersion or dispersion may be included.1/1.

Examples of high boiling point organic solvents include phenol derivatives, phthalates, phosphates, citric esters, benzoates, alkylamides, II old esters, trimesic esters, etc. that do not react with the oxidized form of the developing agent. An organic solvent having a temperature of 1°C or higher is used.

Anionic surfactants, nonionic surfactants, and cationic surfactants are used as dispersion aids when hydrophobic compounds are dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using machines or ultrasound. Surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of the color photographic material of the present invention, causing color turbidity or reducing sharpness. Color antifoggants are used to prevent deterioration and graininess from becoming noticeable.

The color antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers.

In order to prevent the hydrophilic colloid layers such as the protective layer and the intermediate layer of the silver halide photosensitive material of the present invention from capri due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light, ultraviolet rays are used. It may also include an absorption side.

The silver halide photographic material of the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer, if necessary. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

A matting agent is added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention for the purpose of reducing the gloss of the light-sensitive material, increasing the ease of writing, and preventing the light-sensitive materials from sticking together. can be added.

A lubricant can be added to reduce the sliding friction of the silver halide photographic material of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to the silver halide photosensitive material of the present invention. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used for the colloid layer.

The silver halide photographic light-sensitive material of the present invention has a photographic emulsion layer and/or
Other hydrophilic colloid layers may contain various additives for the purpose of improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitizing). Surfactants are used.

The silver halide photographic light-sensitive material of the present invention has a photographic emulsion layer, and other layers include a baryta layer or a flexible reflective support such as paper laminated with α-ole7 rain polymer, synthetic paper, cellulose acetate, cellulose nitrate, It can be applied to films made of semi-synthetic or synthetic polymers such as polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as lath, metal, and ceramics.

The silver halide photographic material of the present invention can be improved in adhesion, antistatic properties, and dimensional stability directly or on the surface of the support after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary. , 1 or 2 for improving abrasion resistance, hardness, antihalation properties, friction properties and/or other properties
It may be applied through the above undercoat layer.

When coating the silver halide photographic light-sensitive material of the present invention, a thickener may be used to improve coating properties.Coating methods include extralan coating, which allows two or more layers to be coated simultaneously; Curtain coatings are particularly useful.

The silver halide photographic material of the present invention can be exposed to electromagnetic waves in a spectral region to which the emulsion layer constituting the silver halide photographic material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps,
Light emitted from phosphors excited by mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams, X-rays, gamma rays, alpha rays, etc. , any known light source can be used.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, or better exposures of 1 second or longer are possible. The exposure may be performed continuously or intermittently.

An image can be formed using the silver halide photographic material of the present invention by performing cuff development, which is known in the art.

The aromatic @primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol-based and 11-7-dinidine diamine-based derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds are generally used in an amount of about 0.0. Concentrations of Ig to about 30 g, preferably about 1 g to about 1 g per color developer
Use at a concentration of 5g.

As a 7mi/phenol developer, for example, 0-7mi7
7 el/-l, p-7 minophenol, 5-amino-2-
These include hydroxytoluene, 2-amino/-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-tmethylbenzene, and the like.

Particularly useful primary aromatic amino color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-noethyl-p-7enylenenoamine hydrochloride;
N-methyl-1]-phenylenediamine hydrochloride, N +
N”)/f lu p7z nylenediamine hydrochloride,
2-7mi/-5-(N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-7/aniline sulfate, N
-Eech N-β-hydroxyethylamine/aniline,
Examples include 4-7 minnow 3-methyl-N, N'-diethylaniline, 4-7 minnow N-(2-nodoxyethyl)-N-ethyl-3-methyl7nyline-9-)luenesulfonate, and the like.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the processing of the color photographic material of the present invention further contains various components normally added to color developers, such as hydroxide. Optionally contain alkaline agents such as sodium, sodium carbonate, and potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, pencil alcohol, water softeners, and thickening agents. You can also do that.

The pH value of this color developer is usually 7 or higher, most commonly about 10 to about 13.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as the bleaching agent used in the bleaching process, and the gold rfG complex oxidizes the metallic silver produced by development and converts it into silver halide, and at the same time colors the uncolored part of the color former. Its properties include aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid to remove iron,
Coordinated with metal ions such as cobalt and shell. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or ami/polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminoniacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [[6] Ethylenediaminetetraacetic acid tetraacetic acid Sodium salt [7]
The bleaching agent used is the sodium nitrilotriacetic acid salt, which is a metal complex salt of an organic acid as described above, and may also contain various additives. Additives include in particular alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, etc.
For use on rodene, it is desirable to contain metal salts, 1-cuttings, and pH 9-cuttings such as borates, oxalates, acetates, carbonates, phosphates, alkylamines, polyethylene oxides, etc. Anything that is known to be normally added to bleaching solutions can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, metabisulfite) Sulfites such as IJium, boric acid, borax, sodium hydroxide, potassium hydroxide, carbonic acid ) potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid,
pH consisting of various salts such as sodium acetate and ammonium hydroxide! Eleven types or two or more kinds of cuts can be included.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain a periosulfate, a thiocyanate, a sulfite, or the like. , the bleach-fixing replenisher may contain these salts and be replenished into the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent may be added. For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

[Specific embodiments of the invention]

The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side.

1st layer: Emulsion layer 6.0mg7100 of cyan coupler A-26 of the present invention
cm2, silver chlorobromide emulsion (containing 58 mol% silver bromide) converted to silver is 4.0B7100cm2, dibutyl 7 crate is 6.0mg/100cm2 and gelatin is 15.0a
The coating was applied so that the coating amount was +g7100cm2.

Second Ni: intermediate layer (UV absorber-containing N) as a UV absorber (2-hydroxy-3-sec-butyl-5-t
-butylphenyl)benz)riazole 5. OB71
00cm2, Nobutyl 7 tallate 3.0B/100c
+a'' and gelatin were coated in an amount of 12.0B7100cm2.

No. 371! 1: Protective layer Gelatin was coated at a coating amount of 8.0B/100c+n2.

The monochrome silver halide photographic material obtained as described above was designated as Sample 1.

Nineteen samples (Samples 2 to 20) were prepared by adding the exemplary compounds of the present invention and comparative compounds to the above Sample 1 in equimolar amounts as the cyan coupler, as shown in Table fjS1.

Comparative compound a (compound described in JP-A No. 59-53846) Comparative compound b (compound described in JP-A-59-87456) After exposing the sample obtained above through an optical wedge according to a conventional method,
The treatment was carried out in the following steps.

[Processing process] Processing temperature Processing time Color development
Bleach fixing at 33℃ for 3 minutes and 30 seconds
Wash with water at 33°C for 1 minute and 30 seconds 33°C
Dry for 3 minutes 50-80
℃ 2 minutes The components of each treatment solution are as follows.

[Color developer] Pencil alcohol 12mQ noethylene glycol 10mQ potassium carbonate 25g sodium bromide
0.6g anhydrous sodium sulfite
2.0g hydroxylamine sulfate m
2.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g water was added to the mixture, and the pH was adjusted to 10.2 with sodium hydroxide.

[3-ball white fixer] Ammonium thiosulfate 120g Sodium metabisulfite 15g Anhydrous sodium sulfite 3g EDTA 12 iron ammonium salt 65g Add water to make 1111 and adjust pH to 6.7-6.8.

The concentrations of Samples 1 to 14 treated above were measured using a densitometer (model KD-7R, manufactured by Konishiroku Photo Industry Co., Ltd.) under the following conditions.

Each of the above-mentioned treated samples was irradiated with a xenon fade meter for 14 days, and the light resistance of the dye image was examined in terms of residual rate.

〔Survival rate〕

Percentage of dye remaining after lightfastness test for initial density 1.0.

The results are shown in the Pt51 table.

As is clear from Table S1, Samples 2 to 18 using the compounds of the present invention have a greater anti-fading effect than Samples 19 and 20 using previously unknown dye image stabilizers. is excellent.

Example 2 All samples were coated in the same manner as in Example 1 except that the cyan coupler was changed to ^-2.
40) was created. After exposing each sample to light in the same manner as in Example 1,
Example 1 except that the composition of the color developer was changed as follows.
The sensitivity was measured using the method described in . Furthermore, the treated sample was subjected to a light resistance test in the same manner as in Example 1, and the results shown in Table 2 were obtained.

[Color developer]

Bennol alcohol 10I111 diethylene glycol 10m & potassium carbonate
25g sodium bromide 1.
OI? Anhydrous sodium sulfite 2.0g Hydroxyamine sulfate 2.5g N-ethyl-N-β
-1: Add 4.0g of droxyethyl-3-methyl-4-aminoaniline sulfate to 1
1 and adjusted to pH 10.2 with sodium hydroxide.

Below - White Table 2 Table 2 also shows the excellent anti-fading effect of the dye image stabilizer of the present invention.

Example 3 A cyan coupler and a dye image stabilizer were combined as shown in Table 3 and applied in exactly the same manner as in Example 1.
0 was created. Each sample was processed as described in Example 1 to determine sensitivity. Furthermore, the treated sample was subjected to a light resistance test in the same manner as in Example 1, and the results shown in Table 3 were obtained.

Table 3 below shows that the combination of the cyan coupler of the present invention and the dye image stabilizer of the present invention significantly improves the light resistance of the colored dye.

Example 4 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor silver halide photographic light-sensitive material, and sample 61 was obtained.

1st layer: blue-sensitive silver halide emulsion layer α-pivaloyl-a-(2,4
-dioxo-1-pencylimidazolidin-3-yl)
-2-chloro-5-[γ-(2,4-monoamylphenoxy)butyramide 1 acetanilide 6.8II
+g/100cm2, blue-sensitive silver chlorobromide emulsion (silver bromide 8
5 mol%) converted to silver is 3.2 mg/100c
m2, butyl 7 tallate 3.5mg/100cm
+2 and gelatin were coated at 13.5 mg/100 cm2.

21st even: Intermediate layer 2.5-no=octylhydroquinone 0.5B7
100cm”, 0.5mg/10 dibutyl 7-thaletate
0cm2 and gelatin were coated at 9.0mg/100cm2.

Third layer: green-sensitive silver dendenide emulsion layer 1-(2,4,6-)lichloro7enyl)-3-(2-chloro-5-octadecenylsuccinimideanilino)-5 as magenta coupler -5.0ml of pyrazolone
F/ 100c+s2, green-sensitive silver chlorobromide emulsion (silver bromide 8
0 mol%) converted to silver is 2.5+B/100c
m”, 3.0 mg of dibutyl 7-thaletate/100 cm
” and gelatin were coated to give 12.0+B/100cm2.

4th layer: intermediate layer UV absorber 2-(2-hydroxy-3-5ea--
ff-5-t-butylphenyl)benzotriazole7. 0mg/100cm", di-butyl 7-thalet to 6.Os+g/100cm2.2. Established.

5th layer: red-sensitive silver halide emulsion layer cyan coupler of the present invention ^-27
4.8eel? /10100e, red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted to silver: 3.0 mg/
1005112, tricresyl phosphate 3.5
mg/100cm2 and gelatin at 11.5 rs
The coating was applied to give a weight of 100 g/100 cm2.

6th/I: Middle class A layer composed of exactly the same composition as the fourth layer.

7th scrap: Protective layer gelatin was coated to give a coating thickness of 8.0+ag/100cm2.

In the above sample 61, the dye image stabilizer of the present invention was added to No. 'Jl in the proportions shown in Table 4, and multilayer sample 6
Samples Nos. 2 to 70 were prepared, exposed and processed in the same manner as in Example 1, and then subjected to a mold light test (irradiated to a xenon fade meter for 16 days). The results are also shown in Table 4.

Table 4 (margin below) Table 4 (margin below) From these results, the dye image stabilizer of the present invention is effective in stabilizing the dye image of the cyan coupler of the present invention, and the results increase as the amount added increases.

In addition, Samples 62 to 70 had extremely small discoloration of the dye images in the light emission test compared to Sample 61. Furthermore, in the samples of the present invention, discoloration and fading of the cyan dye were extremely small;
After the mold light test, the overall color photographic material had good color balance with the yellow and cyan couplers, and maintained extremely good color reproducibility.

Claims (1)

[Scope of Claims] A silver halide photograph characterized by containing at least one cyan coupler represented by the following general formula [I] and at least one compound represented by the following general formula [II] photosensitive material. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 and R_2 are hydrogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, alkoxy groups, aryloxy groups, acylamino groups, and carbamoyl groups, respectively. , represents a sulfonamide group, a sulfamoyl group or a ureido group. R_3 represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, or a heterocyclic group. Further, R_2 and R_3 may be combined with each other to form a 5- or 6-membered ring. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. [In the formula, R_4 and R_5 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R_7 is a Represents an alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group. R_6 represents a substituent, and l represents 0 or an integer of 1 to 4. J is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, or ▲ Mathematical formulas, There are chemical formulas, tables, etc. Represents ▼, and m represents 0 or 1. R_8 and R_9 each represent a hydrogen atom or an alkyl group, and may be the same or different. Also R_4 and R
_5 may be combined to form a 5- or 6-membered ring. l
When is 2 or more, multiple R_6 may be the same or different. Furthermore, R_6 is R_4 and/or R_5, and R
A 5- or 6-membered ring may be formed with the nitrogen atom adjacent to _4 and R_5. ]