JPH02297547A - Silver halide photographic sensitive material containing novel cyan coupler - Google Patents

Abstract

PURPOSE:To improve color developability and to obtain a high sensitivity and high color developing density by incorporating specific cyan couplers into the above material. CONSTITUTION:At least one of the cyan couplers expressed by formula I are incorporated into at least one layer of silver halide emulsion layers. In the formula I, A, B respectively denote an org. group to be combined with an imidazole ring via a carbon atom, nitrogen atom, oxygen atom or sulfur atom; J denotes -CO-, -CS- or -SO2-; R2 denotes an alkyl group, alkenyl group, etc.; R1 denotes a hydrogen atom, alkyl group, alkenyl group, aryl group. The fresh two-equiv. couplers are obtd. even with the imidazole base uncleus which is the novel base uncleus as the cyan coupler in this way. The silver halide color photographic sensitive material contg. the novel two-equiv. cyan couplers having the excellent color developability is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material containing a novel two-equivalent cyan coupler.

[Background of the invention]

Silver halide color photographic materials generally use so-called dye-forming couplers, which form dyes by reacting with a light-sensitive silver halide emulsion and an oxidized color developing agent.

Among these cyan couplers, phenols or naphthols have traditionally been used, for example, in U.S. Patent 2,
No. 369.929, No. 2,474.293, No. 2,8
95.826 etc.

However, cyan dye images obtained from phenols or 7-tols have had serious problems in color reproduction. That is, the short wavelength side of the absorption spectrum of the coloring dye is poorly cut, and the green part and part of the blue part also have unnecessary absorption. As a result, the current situation is that the color reproducibility of color paper and universal photosensitive materials, which lack a lot of correction means, is considerably deteriorated.

Therefore, the present inventors proposed a cyan coupler having a novel mother nucleus in EP 249453, Japanese Patent Application No. 134144/1983, and the like. These couplers have better spectral absorption characteristics of the cyan dye formed than conventional phenol or naphthol type cyan couplers, and can greatly improve color reproducibility.

On the other hand, so-called 2-equivalent couplers, which have a group at their active site that can be separated during a coupling reaction, can reduce the amount of silver and easily increase sensitivity. It is known in the art that it is advantageous in improving image sharpness.

By selecting this leaving group, it is possible to obtain couplers with various properties such as development inhibiting properties, development accelerating properties, bleach accelerating properties, and dye releasing properties. It plays an important role in development.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a new two-equivalent coupler for imidazole core, which is a new core as a cyan coupler, and thereby to provide a new cyan coupler with high color development. An object of the present invention is to provide a silver halide color photographic light-sensitive material containing a novel 2-equivalent cyan coupler having extremely excellent coloring properties.

[Structure of the invention]

The above objects of the present invention have been achieved by a silver halide photographic material in which at least one silver halide emulsion layer contains at least one cyan coupler represented by the following general formula CI).

General formula CI) In the formula, A and B each represent an organic group bonded to the imidazole ring via a carbon atom, nitrogen atom, oxygen atom or sulfur atom, and J is -Co-, -C3- or -SO, -, and R2 represents an alkyl group, alkenyl group, alkoxy group, alkylamino group, aryl group, aryloxy group or anilino group. R represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and may be combined with R8 to form a 5- to 7-membered nitrogen-containing heterocycle; in this case, R
, represents a simple bond.

The present invention will be explained in more detail below.

In the above general formula (I), the organic groups represented by A and B via carbon atoms include alkyl groups (e.g., methyl, i-propyl, t-methyl, trifluoromethyl,
Benzyl, 3-(4-aminophenyl)propyl, allyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsulfonylethyl, 3-(4-(4-
dodecyloxybenzene)sulfonamidophenyl]furovir, l-methyl-2-[(2-year-old cutyloxy-5
-t-octyloxy,)sulfonamidophenyl]
Ethyl, l-methyl-2-(2-year-old ctyloxy-5-
(2-octyloxy-5-t-octylphenylsulfonamide) phenylsulfonamide] ethyl, 2-[
2-octyloxy-5-(2-octyloxy-5-
(t-octylphenylsulfonamido) phenylsulfonamido]ethyl, etc.), aryl groups (e.g., phenyl, naphthyl, 2,4-dichlorophenyl, 2-hydroxy-5-methylphenyl, 2-acetamidophenyl,
2-Methanesulfonamidophenyl, 2-phthanamidophenyl, 2-(N,N-dimethylsulfamoylamino)phenyl, 2-(4-dodecyloxybenzenesulfonamido)phenyl, 2-C2-(2,4 -G-t
-amylphenoxy)hexanamide]phenyl, 2-
(2-year-old ctyloxy-5-t-octylphenylsulfonamidolbamoylphenyl, 4-cyanophenyl, 4-carboxyphenyl, 4-ethoxycarbonylphenyl, etc.),
Examples include a heterocyclic group (eg, 4-pyridyl, 2-benzimidazolyl, etc.), a cyano group, a carboxyl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl' group, and the like.

Examples of organic groups via a nitrogen atom include acylamino groups (eg, acetamide, benzamide, 2.

4-di-t-amylphenoxyacetamide, 2,4-
dichlorobenzamide, etc.), alkoxycarbonylamino groups (e.g., methoxycarbonylamino, propoxycarbonylamino, L-butoxycarbonylamino, etc.)
, aryloxycarbonylamino 7 groups (e.g. phenoxycarbonylamino), sulfonamide groups (e.g.
methanesulfonamide, octanesulfonamide, benzenesulfonamide, 4-dodecyloxybenzenesulfonamide, etc.), anilino groups (e.g., phenylamino, 2-chloroanilino, 2-chloro-4-tetradecanamidoanilino, etc.), ureido groups ( For example, N-methylureido, N-butylureido, N-phenylureido, N,N-dibutylureido, etc.), sulfamoylamino groups (for example, N,N-diethylsulfamoylamino, N-phenylsulfamoyl amino, etc.), amino group (
Examples include unsubstituted amino, N-methylamino, N,N-diethylamino, etc.), heterocyclic groups (eg, 3,5-dimethyl-1-pyrazolyl, 2,6-dimethylmorpholino, etc.), and the like.

Examples of organic groups via an oxygen atom include alkoxy groups (e.g., methoxy, ethoxy, neepropoxy, butoxy,
71
phenoxy, 2,4-dichlorophenoxy, 4-(2-ethylhexanamido)phenoxy, etc.), silyloxy group (
For example, trimethylsilyloxy, dimethylphenylsilyloxy, dimethyl-butylsilyloxy, etc.),
Examples include heterocyclic oxy groups (eg, tetrahydropyranyloxy, 3-pyridyloxy, 2-(1,3-benzimidazolyl)oxy), and the like.

Examples of organic groups via a sulfur atom include alkylthio groups (for example, methylthio, ethylthio, butylthio, 3-
(4-(4-dodecyloxybenzene)sulfonamidophenyl]propylthio, 4-(2-butoxy-5-t
-octylphenylsulfonamide middlethio, etc.), arylthio groups (e.g., phenylthio, 2-naphthylthio,
2.5-dichlorophenylthio, 4-dodecylphenylthio, 2-butoxy-5-t-octylphenylthio, etc.), heterocyclic thio groups (e.g., 2-pyridylthio, 2-(
1.3-benzoxasilyl)thio group, ■-hexadecyl 1,2.3.4-tetrazolyl-5-thio group, l-(
3-N-octadecylcarbamoyl)phenyl-1.2
, 3,4-tetrazolyl-5-thio, etc.).

Here, at least one of A and B is preferably an aryl group.

The alkyl group represented by R1 and R2 has 1 carbon number
-18 is preferred and may be linear or branched. For example, methyl, ethyl, i-propyl, butyl, t-
Examples include groups such as butyl, hexyl, octyl, sec-dodecyl, and octadecyl. In addition, for the alkyl group,
Also included are cycloalkyl groups such as cyclopentyl and cyclohexyl.

Examples of the alkenyl group include propenyl, butenyl, octenyl, oleyl, and the like.

Examples of the alkyl moiety of the alkoxy group and alkylamino group represented by R include the same alkyl groups as the alkyl groups represented by R1 and R.

The aryl group represented by R and R is preferably a phenyl group or a naphthyl group, and the same applies to the aryl moiety of the aryloxy group or anilino group represented by R.

Alternatively, either of the groups represented by A and B may contain a polymer residue having a repeating unit.

The alkyl group, alkenyl group, and aryl group represented by R1 and R2 may have a substituent, such as a halogen atom (e.g., fluorine, chlorine, bromine, etc.), a cyano group, a hydroxyl group, a sulfo group, a carbonyl group. , alkyl groups, alkoxy groups (e.g., methoxy, ethoxy, propoxy, butoxy, octyloxy, etc.), aryl groups, aryloxy groups (e.g., phenoxy, naphthyloxy, etc.), acyloxy groups (e.g., acetyloxy, propionyloxy, benzoyl) oxy, etc.), acylamino groups (e.g., formamide, acetamide, benzamide, etc.),
Sulfonamide groups (e.g., methanesulfonamide, benzenesulfonamide, etc.), sulfamoyl groups (e.g., sulfamoyl, methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl groups (e.g., methylsulfonyl, octylsulfonylboxyl groups, sulfamoyl groups, etc.) group, nitro group, alkylthio group (e.g., ethylthio, octylthio, etc.), arylthio group (e.g., phenylthio), carbamoyl group (e.g.,
ethylcarbamoyl, dimethylcarbamoyl, phenylcarbamoyl, etc.), alkoxycarbonyl groups (e.g.
methoxycarbonyl, butoxycarbonyl, etc.), sulfinyl groups (eg, methylsulfinyl, phenylsulfinyl, etc.), heterocyclic groups (eg, pyrazolyl, triazolyl, etc.), and the like. These substituents may be further substituted with these substituents, in which case the substituents may be the same or different.

Also, R1 is simply a bond and combines with R, making a total of 5 to 7
A nitrogen-containing heterocycle having members J may be formed, and in addition to J, the ring may further contain one co-, -cs-, -so. - may have a group such as -, and may have a hetero atom such as N, S, O, etc.

Ino is a group represented by Ntl J R2,
Among these, especially -NHCORl, NHSO□R2
It is a group represented by R2 is R in general formula CI),
represents the same thing as. Particularly preferred are halogen-substituted alkyl groups, such as chlorine- or fluorine-substituted alkyl groups, carboxyl- or sulfo-substituted alkyl groups, phenyl groups, and substituted phenyl groups.

Examples of the group include groups represented by the following general formula.

,−゛, -8.

"x゛"' In the formula, These may also form a fused ring with a benzene ring, naphthalene ring, or other nitrogen-containing heterocycle. Representative examples of these rings include succinimide group, glutarimide group, hydantoinyl group, urazolyl group, oxazolonyl group, thiohydantoinyl group, and the like.

Among the compounds represented by the general formula [I], representative ones include the general formulas (![), (I[[) and (IV)].

General formula (n) General formula CIII) General formula (IV) In general formulas (n) to (IV), R11, R1,, R
13, R. and Rlfi each represent a substituent, L represents an oxygen atom or a sulfur atom, and n represents an integer of 0 to 5.

R1 and R, each represent R in the general formula (1) above.
．． and R.

Next, the compound of general formula (IF) will be explained in more detail.

In general formula (If), R. and R1! The substituent represented by is not particularly limited, but for example, as a halogen atom and an alkyl group represented by cyano, hydroxy, nitro, carboxy, alkyl, alkoxy, carbamoyl, sulfamoyl, acyl, acyloxy, alkoxycarbonyl group R11 and R12, , a straight chain or branched alkyl group having 1 to 22 carbon atoms is preferred, such as methyl, ethyl, butyl, dodecyl, and the like. These alkyl groups also include cycloalkyl groups such as cyclohexyl groups, and may be substituted. Preferred substituents include a halogen atom, a hydroxy group, a carboxy group, a cyano group, a sulfo group, and a group having 1 carbon atom.
-22 alkoxy groups and the like.

The alkoxy group is preferably a linear or branched alkoxy group having 1 to 22 carbon atoms, such as methoxy, ethoxy, i-propyloxy, octyloxy, and dodecyloxy groups.

Examples of the carbamoyl group include unsubstituted alkylcarbamoyl groups such as ethylcarbamoyl and dodecylcarbamoyl groups, and substituted alkylcarbamoyl groups such as diethylcarbamoyl, butyloxypropylcarbamoyl and dodecyloxyglobylbamoyl groups.

Similarly, regarding the sulfamoyl group, unsubstituted alkylsulfamoyl groups such as ethylsulfamoyl, diethylsulfamoyl, and todenrusulfamoyl groups, substituted alkylsulfamoyl groups such as dodecyloxyprobylsulfamoyl group, etc. Can be mentioned.

Examples of the arylcarbamoyl group include a phenylcarbamoyl group and a substituted phenylcarbamoyl group, and examples of the arylsulfamoyl group include a phenylsulfamoyl group and various substituted phenylsulfamoyl groups.

In addition, acyl groups such as acetyl, benzoyl, butanesulfonyl, benzenesulfonyl groups, acyloxy groups such as acetoxy, lauroyloxy, butanesulfonyloxy groups, ethoxycarbonyl, i-propyloxycarbonyl, 2-ethylhexyloxycarbonyl groups, etc. Examples include alkoxycarbonyl groups. Also included are anilino groups such as anilino and dibromoanilino groups. The NHCORla group represents an alkylamide group having 1 to 22 carbon atoms, and representative examples of the unsubstituted alkylamide group include acetamide, butanamide, laurylamide, stearylamide groups, and the like.

Further, it may be an alicyclic amide group such as a cyclohexanecarponamide group, a branched structure such as a 2-ethylhexaneamide group, or may contain an unsaturated bond.

Examples of the substituted alkylamide group include halogen-substituted alkylamide groups such as monochloroacetamide, trichloroacetamide, and perfluorobutanamide groups, as well as halogen-substituted alkylamide groups such as monochloroacetamide, trichloroacetamide, and perfluorobutanamide groups;
Examples include phenoxy-substituted alkylamide groups such as amylphenoxy)pentanamide, α-(2,4-di-t-acylphenoxy)acetamide, and 0-chlorophenoxymyristic acidamide groups.

In addition, the NHCORls group represents an arylamide group, typically an unsubstituted arylamide group such as a pentzamide or naphthamide group, and a substituted arylamide group such as
Alkyl-substituted pennzamide groups such as p-t-'butylbenzamide and p-methylbenzamide groups, alkoxy-substituted pennzamide groups such as p-methoxybenzamide and 0-dodecyloxybenzamide groups, p-acetamidobenzamide, -lauroyl Amidobenzamide, m-(
Typical examples include amide-substituted pennzamide groups such as 2,4-di-t-amylphenoxyacetamide) penzamide groups, and sulfonamide-substituted pennzamide groups such as 0-hexadecanesulfonamidebenzamide and p-butanesulfonamidebenzamide groups. It is mentioned in

The NHCOORra group represents a substituted or unsubstituted alkoxycarbonylamino group having 1 to 22 carbon atoms, and typical examples include etquincarbonylamino, x-;7'lopoxyluponylamino, octyloxycarbonylamino, decyloxycarbonyl, Examples include methquinethoxycarbonylamino group. The NHCOOR1s group also represents an aryloxycarbonyl group, and a typical example thereof is a phenoxycarbonyl group.

represents a group, typically dimethylcarbamoylamino,
Examples include diethylcarbamoylamino group.

-NH30,R□, the group represents an alkylsulfonamide group or an arylsulfonamide group.

Examples include unsubstituted alkylsulfonamide groups having 1 to 22 carbon atoms such as alkylsulfonamide, middle phonamide, butanesulfonamide, and dodecanesulfonamide groups, and substituted alkylsulfonamide groups such as benzylsulfonamide groups.

Further, as the arylsulfonamide group, unsubstituted arylsulfonamide groups such as benzenesulfonamide and naphthalenesulfonamide groups, p-toluenesulfonamide, 2,4.6-dodecylbenzenesulfonamide,
p-dodecylbenzenesulfonamide group, p-dodecyloxybenzenesulfonamide,
Mention may be made of substituted arylsulfonamide groups such as alkoxy-substituted benzenesulfonamide groups such as butyloxybenzenesulfonamide groups.

Typical examples include dimethylsulfamoylamino,
Dialkyl sulfur 7 such as dibutylsulfamoylamino group
An amoylamino group is preferred.

Among the compounds represented by the general formula (U), the following general formulas (V) and (Vl) are exemplified as preferable compounds.

General formula (V) General formula (Vl) General formula [v] and (Vl) j: u%-t-, R+++
R+z+R , , R , and n are R , , R , , in general formula (II).

Each has the same meaning as R1, R, and n.

m ii O - 4 integer 'i 0R is an alkyl group, the alkyl group represented by R11 has a carbon atom number of 1
-32 linear or branched alkyl groups are preferred, and also include cycloalkyl groups such as cyclohexyl groups. Further, these alkyl groups may be substituted, and representative examples of 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. I can do it.

The aryl group represented by Rta is preferably a phenyl group, and the phenyl group may be substituted with a nitro group, an amide group, a sulfonamide group, or the like.

Also, NHR+a is one NHCOR, M group, N
HCOOR r a group is R1 in general formula (IF)
．． and R,7, respectively.

Among the compounds represented by the general formulas (V) and (Ml), one of R11 in the general formulas (V) and (Vl) is a group represented by 1NHRts,
and the general formula [■] present at the 0-position with respect to the imidazole ring
Examples include compounds represented by:

General formula [■] In the formula, R , , R , , RtasR (, R2 and m each have the same meaning as in general formula (V), and R11 has the same meaning as R. -NHR r m The presence of the group provides better heat resistance as well as absorption of coloring dyes.

Next, the compound of general formula [111) will be explained in more detail.

In the general formula (I[[), R1! , R, , R2 and n
are Rdz, R1, R2 in the general formula [:n)i::
and n, and each of R13 and R8 is a hydrogen atom, an alkyl group, or an aryl group. Also, R
33 and RIG may be bonded to each other to form a heterocycle.

As the alkyl group or aryl group represented by R3 or R1, the alkyl group or aryl group explained in the above general formula [■] and (Vl) can be specifically mentioned.

The heterocycle formed by combining RI3 and RI4 is preferably a 5- or 6-membered heterocycle, and these heterocycles may have a substituent and may also be fused with a carbon ring.

Among the compounds represented by the general formula CIII), a more preferable compound is one in which one of R3 in the general formula (I Existing compounds represented by the general formula [■] can be mentioned.

General formula [■] [In the formula, R12, R13, R1, R1 and R7 are R Its R13, R14 in the general formula (I[[)]
, R1 and R3, respectively, and R1, and m
are Rlm and m in the general formula (V) and [■]
are synonymous with each other. ] Next, the compound of general formula (IV'l) will be explained in more detail.

In the general formula (mV), Rr2, R1, R1 and n have the same meanings as R38, R1, R2 and n in the general formula (II3), respectively, and R1 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. represents.

As the alkyl group and aryl group represented by Rdz, the alkyl group and aryl group explained in the above general formulas (V) and (VI) can be specifically mentioned.

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

Among the compounds represented by the general formula (IV), a more preferable compound is the general formula [■] in which one of R1 is -NH
Examples include compounds represented by the general formula [■], which is a group represented by R1m and is present at the 0-position with respect to the imidazole ring.

General formula (IV) In the formula, R1! , R16, L%R1 and R7 have the same meanings as Rdz, R, I, R, and R2 in the general formula (IV), respectively, and RIM and m have the same meanings as in the general formula [v
] and [■] R1. and m have the same meaning, respectively.

The compound represented by the general formulas CI) to [匡] (hereinafter referred to as the coupler of the present invention) is imidazole R.

It is characterized by having a group represented by -N J R2 at the 4-position, which provides excellent color development and can provide extremely high sensitivity and maximum density.

Therefore, it is possible not only to reduce the amount of silver halide contained in the photographic emulsion layer, but also to be suitable not only for normal processing but also for rapid processing. Furthermore, it has excellent solubility in high-boiling organic solvents and dispersion stability in silver halide emulsions.

``Additionally, as other features of the coupler of the present invention, the formed dye has a high molar absorption coefficient, exhibits sharp absorption without unnecessary absorption, and has excellent fastness against light and heat. are doing.

Furthermore, the coupler of the present invention has a weak oxidizing power or is fatigued; it also has the feature that there is almost no decrease in color density even when it is treated with a bleaching solution.

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

The cyan coupler of the present invention can be synthesized according to various methods, and typical synthesis examples are shown below.

Synthesis Example 1 (Synthesis of Compound Example 2) Synthesis 5.44 g of 0-(α-(2,4-di-t-amylphenoxy)hexaneamiF)-a-bromoacetophenone was dissolved in 30IIa of chloroform, and the mixture was heated to 0.5 g at room temperature. 1 mol free benzamidine chloroform solution 40van
drip. After stirring for 1 hour, chloroform was distilled off under reduced pressure.
Dissolve in 200mff of ethanol, wash with 50ml of 5% potassium carbonate aqueous solution, further wash with 5QmQ of water, dry over magnesium sulfate, and distill off the ethanol. By fractionating using a silica gel column (ethanol:hexane-1:l) and distilling off the solvent, 4.2g (7 ml) of solid was obtained.
4% yield) was obtained.

2-phenyl-4(o-(y-(2,4-di-t-amylphenoxy)hexaneamido)phenyl)-5-(2
Synthesis of -acetylphenylazo)imidazole 2.84 g of 0-aminoacetophenone was dissolved in dilute hydrochloric acid, and 1.45 g of sodium nitrite was added thereto little by little while keeping the internal temperature below 5°C. The solution is completely diazotized and becomes a pale yellow transparent liquid.

Apart from this, the aforementioned 2-phenyl-4-(o-(a-
(2,4-di-t-amylphenoxy)hexaneamide) 11.3 g of phenylcoimidazole was added to 200 g of pyridine.
While keeping the solution dissolved in si2 at 5° C. or below, a diazo solution also kept at 5° C. or below was added dropwise thereto while ensuring that the internal temperature did not rise above 1060°C.

After the dropwise addition was completed, stirring was continued for 30 minutes at a temperature of 10°C or less. After the reaction, the reaction solution was poured into 1.5Q of ice water to precipitate crystals. It was purified by column chromatography to obtain an orange amorphous solid (8.7 g). This substance was an orange-red dye (in methanol) with an absorption maximum at 476n.

8.50 g of the above dye was dissolved in 500 md of alcohol, and 0.3 g of palladium-carbon catalyst was added thereto, followed by catalytic reduction at normal pressure. Since hydrogen absorption stopped when the theoretical amount of hydrogen was absorbed, the palladium-carbon catalyst was removed by filtration, and the filtrate was concentrated. The precipitated solid was thoroughly washed with acetonitrile to obtain 6.54 g of a crude amino compound. This amino compound was used as it was in the next reaction without being purified.

2.0 g of the amino compound obtained by the above method was reacted with 0.74 g of pentafluoropropionic anhydride in acetonitrile for about 2 hours at room temperature. After removing the acetonitrile under reduced pressure, the concentrate was dissolved in ethyl acetate and washed with water, then with 5% aqueous sodium bicarbonate solution, and then with dilute hydrochloric acid (1-2%). After the ethyl acetate layer was dehydrated with magnesium sulfate, the magnesium sulfate was filtered off and the ethyl acetate layer was concentrated.

This residue was purified by column chromatography.

A caramel-like amorphous solid was obtained by thoroughly drying the candy-like substance under reduced pressure.

(Yield: 1.42 g) It was confirmed to be Compound 2 by NMR and Mass spectra.

Synthesis Example 2 (Synthesis of Compound Example 17) 2.0 g of the active site amino compound obtained by the above method was boiled and refluxed for 3 hours with 0.37 g of succinic anhydride in ethyl acetate 50III2. After cooling, 0.2 mQ of concentrated sulfuric acid was added, and the mixture was boiled and refluxed again for 1.5 hours. After cooling, place in ice water.
Furthermore, 100 m of ethyl acetate (2) was added and extracted with ethyl acetate. The ethyl acetate layer was thoroughly washed with water, then dried with magnesium sulfate and concentrated. The residue was purified by column chromatography to obtain 1.83 g of amorphous solid. Obtained.

It was confirmed by NMR and mass spectra that it was the desired product.

Synthesis Example 3 (Synthesis of Compound 23) 2-(o-acetamidophenyl)-4-(o-(α-
2,4-di-t-amylphenoxy)hexanamide)
Phenyl]-imidazole 5.5g in chloroform 80g
1.24 g of N-chlorosuccinimide dissolved in m+2
was added and allowed to react at room temperature for 2 days. The reaction solution was poured into water, and the chloroform layer was further washed with water 2 to 3 times, then dehydrated and concentrated, leaving a candy-like substance. Recrystallization from acetonitrile yielded 4.3 g of the 5-chlor compound as a whole.

3.0 g of the above chloride was refluxed with 1.35 g of N-benzylhydantoin potassium salt in acetonitrile for 30 hours. After cooling, it was poured into ice water and extracted with ethyl acetate.

The ethyl acetate layer was washed with water and then dehydrated with anhydrous magnesium sulfate. The oil obtained by concentration was purified by column chromatography to obtain 0.43 g of the target product in the form of candy.

The cyan coupler of the present invention is used in a silver halide emulsion layer, mainly a red-sensitive silver halide emulsion layer, and the amount added is 2X 10-3 to 8XIO-' per mole of silver halide.
Mol, preferably IX 10-" to 5x 10-'-
It is within the range of T.

Various methods can be used to incorporate the cyan coupler of the present invention into a silver halide emulsion layer. Phenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate) and/or high boiling point organic solvents with a boiling point of 150°C or higher and/or a boiling point of 30~30°C
It is dissolved in a low boiling point organic solvent (for example, ethyl acetate, butyl acetate, propion is ethyl, secondary butyl alcohol, methyl isobutyl ketone, methyl cellosolve acetate, etc.) at 150° C., and then dispersed in a hydrophilic colloid. Usually, it is preferable to use a mixture of the above-mentioned high boiling point organic solvent and low boiling point organic solvent.

The silver halide grains used in the silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention are not particularly limited; , silver chloride, silver chlorobromide containing silver chloride, or silver iodide.

Particularly preferred as such silver halide grains are silver halide grains for rapid processing having a silver chloride content of 90 mol % or more.

The silver halide grains for rapid processing have a silver chloride content of 90 mol% or more, a silver bromide content of 5 mol% or less,
The silver iodide content is preferably 0.5 mol% or less. More preferred is silver chlorobromide having a silver bromide content of 0.1-1.0 mol%.

These silver halide grains for rapid processing may be used alone or in combination with other silver halide grains having different compositions. Further, it may be used in combination with silver halide grains having a silver chloride content of less than 10 mol %.

Further, in the silver halide emulsion layers containing silver halide grains for rapid processing, the ratio of the silver halide grains for rapid processing to the total silver halide grains contained in these emulsion layers is preferably 6. ( ) weight % or more, more preferably 80 weight % or more.

The silver halide used in the present invention may be a polydisperse emulsion in which the average grain size is distributed over a wide range, but a monodisperse emulsion is preferred.

These silver halide-containing emulsions may be chemically sensitized with active gelatin, a sulfur sensitizer, a selenium sensitizer, a reduction sensitizer, a noble metal sensitizer, or the like.

The silver halide used in the present invention may be optically sensitized by adding an appropriate sensitizing dye in order to impart photosensitivity in a desired wavelength range.

The silver halide photographic material of the present invention having the above structure can be, for example, color negative and positive films, color photographic paper, and the like.

The silver halide color photographic material of the present invention, including this color photographic paper, is a multicolor silver halide photographic material, and in order to perform subtractive color reproduction, magenta, magenta, magenta, It has a structure in which silver halide emulsion layers containing yellow and cyan couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and layer order, but the number and layer order are important. It may be changed as appropriate depending on performance and purpose of use.

The specific layer structure of the silver halide color photographic light-sensitive material used in the present invention includes, on a support, a yellow dye image forming layer, an intermediate layer, a magenta dye image forming layer, an intermediate layer, Particularly preferred are those arranged with a cyan dye image forming layer, an intermediate layer and a protective layer.

The silver halide color photographic light-sensitive material of the present invention includes a color antifoggant, an image stabilizer, a hardening agent, a plasticizer, a polymer latex, an ultraviolet absorber, a formalin scavenger-1 mordant, a development accelerator, and a development retardant. , a fluorescent whitening agent, a matting agent, a lubricant, an antistatic agent, a surfactant, etc. can be optionally used.

Various color development processes can be applied to the development process of the silver halide color photographic light-sensitive material of the present invention.

The coupler of the present invention can be used for heat-developable photosensitive materials (for example, JP-A-63
It is also effective as a dye-providing substance for heat-developable photosensitive materials (described in Japanese Patent No. 301033, No. 63-304242, etc.).

When used in a heat-developable photosensitive material, a coupler having a pallast group (preferably a polymer chain is preferred as the pallast group) as a substituent at the active site of the coupler is preferable.

〔Effect of the invention〕

By containing the cyan coupler of the present invention, the silver halide color photographic light-sensitive material of the present invention has excellent color development properties and can obtain high sensitivity and high color density. However, it has excellent robustness.

Example 1 A mixed solution of 6 g of cyan coupler shown in Table 1, 3 g of dibutyl phthalate, and 18 g of ethyl acetate was heated to 60°C to dissolve it. A dispersion liquid was prepared by mixing 10 m2 of a 5% aqueous solution of gelatin containing 10 m2 of a 5% aqueous solution of sulfonate (manufactured by DuPont) and emulsifying and dispersing it with an ultrasonic disperser.

Next, the above dispersion was added to a silver chlorobromide emulsion (containing 99.5 mol% silver chloride) so that the cyan coupler was 30 mol% based on silver, and a hardening agent was added. -dichloro-6
- Sodium hydroxytriazine was added at a rate of 12n+g per gram of gelatin, and then coated on a polyethylene laminate paper support at a coated silver amount of 3 mg/100 cm'.

Each of the silver halide photographic materials thus obtained was subjected to wedge exposure in a conventional manner and then subjected to the following development treatment.

[Processing process]

Processing process Temperature Time Development color development
34.7±0.3℃ 45 seconds bleach fixing
34.7±0.5°0 50 seconds stabilization 30~
Dry for 90 seconds at 34℃ 60-80℃
60 seconds [Color developer] Pure water
800m12 triethanolamine
8g N,N-diethylhydroxylamine
5g potassium chloride 2g
N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfur salt
5g sodium tetrapolyphosphate
2g potassium carbonate 3
0g Potassium sulfite 0.2g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1g Add pure water to bring the total volume to 14, and adjust the pu to 10.2.

[Bleach-fix solution]

Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100md
Ammonium sulfite (40% solution) 27.5
Add mα water to bring the total volume to tQ, and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

[Stabilizing liquid]

5-Chloro-2-methyl-4-isothiazolin-3-one Igl-hydroxyethylidene-1,1-diphosphonic acid 2g Add water to make IQ, and adjust pH to 7.0 with sulfuric acid or potassium hydroxide.
Adjust to 0.

The developed sample was measured using an optical densitometer (PDA-6 manufactured by Konica Corporation).
Sensitivity (Sl) and maximum concentration (DIla
x) was measured. The results are shown in Table-■.

Table 1 However, sl is a relative value when the sensitivity of sample 1 containing comparative coupler c-t is set to 100. (Sensitivity is the logarithm of the exposure amount at a density of fog + 0.1) Comparative coupler C-1 Comparative coupler C-2 As is clear from Table 1, Sample 1. Compared to sample 2, samples 3.4.5 and 6 using the cyan coupler of the present invention have higher sensitivity;
Provides sufficient color density.

Example 2 A mixed solution of 6 g of cyan coupler represented by C-3, 3 g of tricresyl phosphate, and 18 g of ethyl acetate was heated to 60°C to dissolve it, and then this was dissolved in alkanol B. (alkylnaphthalene sulfonate,
The mixture was mixed with 100 m12 of a 5% aqueous gelatin solution containing 10 m12 of a 5% aqueous solution (manufactured by DuPont), and emulsified and dispersed using an ultrasonic dispersion machine to prepare a dispersion.

Next, the above dispersion was added to a silver iodobromide emulsion (containing 6 mol% silver iodide) so that the cyan coupler was 10 mol% based on silver, and 1,2-bis( Sample 7 was prepared by adding vinylsulfonyl)ethane at a rate of 12 mg per gram of gelatin and then coating it on a subbed transparent cellulose triacetate film support at a coating weight of 18 g/100 cm''.

Further, Samples 8 to 12 were prepared in the same manner as Sample 7 except that cyan coupler C-3 was replaced with an equimolar amount of the cyan coupler of the present invention shown in Table 2.

Samples 7 to 12 were each subjected to wedge exposure and then subjected to the following development treatment.

Processing process (38°C) Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing with water
3 minutes 15 fixed arrival
Wash with water for 6 minutes and 30 seconds
3 minutes 15 seconds stabilization 1 minute 30
Second drying The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75g anhydrous sodium sulfite 4°25g hydroxylamine l/2 sulfate 2.0g anhydrous potassium carbonate
37.5g sodium bromide
1.3g nitrilotriscatenic acid trisodium salt (1 hydrate) 2.5g potassium hydroxide 1.0g Add water to make 1Q
and adjust the pH to 10.0 using potassium hydroxide.

[Bleach solution]

Iron (I) ethylenediaminetetraacetic acid Ammonium salt 100g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
IQ, 0+aQ Add water and make 1a
and adjust the pH to 6.0 using aqueous ammonia.

[Fixer]

Ammonium thiosulfate (50% aqueous solution) 162 mQ.

Anhydrous sodium sulfite 12.4g Add water to make la, and adjust to pH-6.5 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5m (2
Konidax (manufactured by Konica Corporation) Add 7.5 mff of water to make 1Q.

The sensitivity and maximum density of the cyan coupler dye image thus obtained were evaluated in the same manner as in Example-1.

Further, the obtained sample was stored for 20 days under the conditions of 85° C. and 60% relative humidity, and the dark fading property was evaluated by determining the residual rate (%) of the cyan dye image at an initial density of 1.0.

The results are also shown in Table-2.

Table 2 S is expressed as a relative value when the sensitivity of sample 7 is set as 100.
tko.

Comparative coupler C-3 As shown in Table 2, the coupler of the present invention has high sensitivity,
It has high color development and also improves dark fading resistance.

Example 3 A silver halide emulsion prepared by the method described in Japanese Patent Application No. 61-31330, that is, a core having a multi-shell structure in which the iodine content decreases from the high iodine shell inside the grain toward the outside. A /shell silver iodobromide emulsion was chemically sensitized according to a conventional method, and a coating solution for each layer containing the following additives was sequentially coated from the support side onto a triacetyl cellulose film to produce a color photosensitive film consisting of 13 layers. The material was prepared. (Sample 13) First layer: antihalation layer Gelatin layer containing black colloidal silver.

Gelatin 2.2 g/+" Second layer; Intermediate layer 2. Gelatin layer containing an emulsified dispersion of 5-di-t-octylhydroquinone.

Gelatin 1.2 g/m" 3rd layer; low sensitivity red-sensitive silver halide emulsion layer average grain size 0.
Monodispersed emulsion (emulsion I) consisting of octahedral silver iodobromide with a diameter of 38 μm and an average normality content of 7.84% (molar ratio)...Silver coverage: 1.8 g/m2 Sensitizing dye I...Silver 1 a x to-' molar sensitizing dye■...
- 1.0% per mole of silver. OX 10-'molar sensitizing dye ■・
... 1 mole of silver. OX 10-'Morsian coupler (C-4)... 0.06 mol per mol of silver Colored cyan coupler (CG-1)... 0.003 mol per mol of silver DIR compound CD- 1)... 0.0015 mol DIR compound (D-2)... 0.002 mol gelatin per 1 mol silver 1.4 g/w'' fJ4 layer; Highly sensitive red-sensitive halogen Silveride emulsion layer average grain size 0
．． A monodispersed emulsion (emulsion ■) consisting of octahedral silver iodobromide with a diameter of 65 μm and an average normality content of 7.37%...Silver cloth'! 1.3 g/m2 Sensitizing dye I... 3 x 10-' mol sensitizing dye ■... per 1 mol of silver
・One mole of silver is equivalent to shite! , 0×1 O-s-E sensitizing dye ■ @1. OX 10-'Morsian coupler (c-5)... 0.02 mol per mol of silver Colored cyan coupler (CC-1)... 0.0015 mol DIR compound (D -2)... o, oot mole gelatin per mole of silver 1. Og/m” 5th layer: Gelatin layer, same as the 2nd intermediate layer.

Gelatin 1. Og/m" 6th layer: Low sensitivity green-sensitive silver halide emulsion layer pore agent -■・
... Coated silver amount 1.5 g/m' sensitizing dye ■... 2.5X 10-'' mole sensitizing dye V per 1 mole of silver
・・1.2X 10-' mol sensitizing dye for 1 mol of silver■・
... 1 mole of silver. OX 10-'mol magenta coupler (M-1)... 0.05 mol per mol of silver Colored magenta coupler (CM-1)... 0.009 mol per mol of silver DIR compound ( D-1)... o, ooio mol per mol of silver DIR compound (D-3)... 0.0030 mol per mol of silver Gelatin 2.0 g/na'' 7th layer; High sensitivity Green-sensitive silver halide emulsion layer pore agent -■・
... Coating amount silver 1.4 g/m' sensitizing dye ■... 1.5X 10-' mol sensitizing dye V per 1 mol silver
... 1 mole of silver. OX 10-'molar sensitizing dye ■・
... 7.0X to-' mole magenta coupler (M-1) for L mole of silver... 0.020 mole for 1 mole of silver Colored magenta coupler (CM-1)... for 1 mole of silver 0.002 mol for DIR compound (D -3)... 0.0010 mol for 1 mol of silver Gelatin 1.8 g/m" 8th layer Same as the intermediate layer 2nd layer, gelatin layer Gelatin 1.Og /m'' 9th layer: Yellow filter layer Yellow gelatin layer containing an emulsified dispersion of colloidal silver and 2,5-di-t-octylhydroquinone.

Gelatin 1.5 g/m' 1st θ layer; low sensitivity blue-sensitive silver halide emulsion layer Monodisperse emulsion (emulsion ■)... Silver coating amount 0.9 g/m'' Sensitizing dye ■... 1 mole of silver Yellow coupler (Y-1)... 0.29 mol gelatin per mol silver 1.9 g/m'' 11th layer: Highly sensitive blue-sensitive emulsion layer Monodispersed emulsion ( Emulsion T1)... Silver coating amount 0.5 g/m' Sensitizing dye ■... t, ox to-' mole per 1 mole of silver Yellow coupler (Y-1)... For 1 mole of silver 0.08 mol DIR compound (D-2) 0.0015 mol gelatin per 1 mol silver 1.6 g/a+" 12th layer: 1st protective layer Silver iodobromide (Agl 1 mol % Average particle size 0 .07 μm) Silver coating amount: 0.5 g/n+1 Gelatin layer containing ultraviolet absorbers UV-1 and UV-2.

Gelatin 1.2 g/m2 13th layer; 2nd protective layer polymethyl methacrylate particles (diameter 1.5 μa+) Ethyl methacrylate: methyl methacrylate: methacrylic acid copolymer particles (average particle size 2.5 μm) Polydimethylsiloxane 51 g/ Gelatin layer containing Ilz and formalin scavenger (HS-1) 1.2 g/-2 gelatin In addition to the above composition, each layer contains a gelatin hardening agent (H-1).
), a surfactant was added.

Samples 14 and 15 were also prepared by applying samples in which the cyan coupler C-5 in the fourth layer was replaced with 0.6 times the molar amount of coupler 27 or 32 of the present invention.

(Additive) C-1 H H Ura M-1 CM-1 rθ ShiUV-t Shi41'ls (suV-2 H3-I H-1 Sensitizing dye I Sensitizing dye n Sensitizing dye ■ Increase Sensitizing Dye ■ Sensitizing Dye V Sensitizing Dye ■ Sensitizing Dye ■ Each sample prepared in this manner was wedge-exposed with white light, and then the following development process was performed to determine the sensitivity and fog.Sensitivity is Fog + 0 The relative sensitivity is expressed as the reciprocal of the exposure amount that gives a density of .5, and the sensitivity of the red-sensitive layer of sample 13 is set as 100.

Further, the developed sample was subjected to a storage test for 20 days under forced deterioration conditions of 85° C. and 60% relative humidity, and the dark fading resistance of the cyan dye image was evaluated based on the image survival rate after deterioration at a density of 1.0. The results are also shown in Table 3.

Processing process (38℃) Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing with water
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
3 minutes 15 seconds stabilization 1 minute 30
Second drying The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine l/2 Tii acid tJ [2.0g anhydrous potassium carbonate 37 .5g sodium bromide
1.3g nitrilotriacetic acid trisodium salt (l hydrate) 2-5g potassium hydroxide Add 1.0g water and lI2
shall be.

[Bleach solution]

Iron(III) ethylenediaminetetraacetic acid Ammonium salt 100g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
10.0m (i water added lQ
and adjusted to pu-6.0 using ammonia water.

[Fixer]

Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 112,
Adjust the pH to -6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5 mff
Konidax (manufactured by Konica Corporation) 7.5m12
Add water to make 112.

As shown above, it can be seen that the sample using the coupler of the present invention has higher sensitivity than the comparative sample.

Example-4 On a transparent polyethylene terephthalate film support,
A heat-developable light-sensitive material was prepared by coating a heat-developable light-sensitive layer having the following structure on support IC.

Benztriazole silver 0.6g Gelatin 3.0g Reducing agent ner
0.97g coupler (43)
10g silver iodobromide (silver equivalent)
0.45g polyvinylpyrrolidone
1.0g benztriazole
0.02g inhibitor zero*
0.01 g hot solvent book 34.5 g After imagewise exposure of the above photosensitive material, the image-receiving material obtained by coating polyvinyl chloride on photographic baryta paper was superimposed, and 1
When thermally developed at 50°C for 1 minute, a good cyan-colored transferred image was obtained on the image-receiving material.

Claims (1)

[Claims] At least one silver halide emulsion layer has the following general formula [
A silver halide photographic material containing at least one cyan coupler represented by I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. represents -CO-, -CS- or -SO_2-, and R_2 represents an alkyl group, alkenyl group, alkoxy group, alkylamino group, aryl group, aryloxy group or anilino group. R_1 represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and may be combined with R_2 to form a 5- to 7-membered nitrogen-containing heterocycle as a whole,
In this case, R_1 represents a simple bond. ]