JPH0462546A - Silver halide photographic sensitive material containing novel cyan coupler - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material good in spectral absorption characteristics of a cyan dye and high in color development density by incorporating a specified cyan coupler in at least one emulsion layer. CONSTITUTION:At least one silver halide emulsion layer contains the cyan coupler represented by formula I in which each of A, B, and D is a substituent combined through C, N, or S with a pyridone ring, and it may be H or halogen; X is H or a group to be released by coupling with the oxidation product of a color developing agent. As the substituent combined through the carbon atom with the pyridone ring, alkyl and aryl groups are enumerated, and as that combined through N, amino and alkylamino or the like groups are enumerated, thus permitting the obtained photographic sensitive material to be good in the spectral absorption characteristics of the formed cyan dye, small in irregular absorption in the wavelength region of green and blue parts, superior in color reproduction performance, and high in cyan dye development density, and therefore, to be enhanced in sharpness by thinning the film.

Description

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

[Background of the invention]

In silver halide color photographic materials, generally,
So-called dye-forming couplers are used which react with a light-sensitive silver halide emulsion and an oxidized color developing agent to form a dye.

Among these, phenols and naphthols have been widely used as cyan couplers, and these are disclosed in, for example, U.S. Pat.
It is stated in the number etc.

However, cyan dyes obtained from phenols and naphthols have had serious problems in color reproduction. In other words, these cyan color-forming dyes have poor cut-off on the short wavelength side of the absorption spectrum, and also have unnecessary absorption, that is, asymmetric absorption, in the green portion or some of the pull portions. Therefore,
To solve this problem, in conventional negative films, asymmetric absorption has been corrected by masking with a colored doubler, but this is undesirable because it causes a decrease in sensitivity. Furthermore, in the case of reversal sensitive materials and color papers, these correction means cannot be used, and the current situation is that color reproducibility is considerably deteriorated.

[Purpose of the invention]

The first object of the present invention is to contain a novel cyan coupler, and to produce a cyan dye that has good spectral absorption characteristics, that is, to be sharp on the short wavelength side, and to have less asymmetrical absorption in the green and blue parts. Our objective is to provide silver photographic materials.

The second object of the present invention is to provide cyan dye with high coloring density.
That is, the object of the present invention is to provide a silver halide photographic material having a cyan coupler with high coloring property.

[Structure of the invention]

The object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has the following general formula CI). This is achieved by a silver halide photographic material containing the cyan coupler shown below.

General Formula [I] In the formula, A, B and D each represent a substituent bonded to the pyridone ring via a carbon atom, nitrogen atom, oxygen atom or sulfur atom. A, B and D may be the same or different.

X represents a hydrogen atom or a group capable of being eliminated by a coupling reaction with an oxidized product of a color developing agent.

[Specific structure of the invention]

Next, the coupler represented by the general formula [I] according to the present invention will be explained.

In general formula (1), A, B and D each represent a substituent bonded to the pyridone ring via a carbon atom, nitrogen atom, oxygen atom or sulfur atom. A, B and D may be hydrogen atoms or halogen atoms.

Substituents bonded to the pyridone ring via carbon atoms include:
Examples include an alkyl group, an aryl group, a cyan group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, and a heterocyclic group.

As substituents bonded to the pyridone ring via a nitrogen atom,
Examples of substituents bonded to the pyridone ring via an amino group, an alkylamino group, a dialkylamino group, an anilino group, a heterocyclic group, and an arsenic oxygen atom include, for example, an alkoxy group,
Mention may be made of aryloxy groups.

Substituents bonded to the pyridone ring via a sulfur atom include:
Examples include an alkylthio group and an arylthio group.

These groups can further have substituents.

The substituents represented by A, B and D will be described in more detail.

The alkyl group is preferably a straight chain or branched alkyl group having 1 to 22 carbon atoms, such as a methyl group, an ethyl group, a butyl group, a dodecyl group, and the like. These alkyl groups include cycloalkyl groups such as cyclohexyl groups, and may be substituted.

Preferred substituents include a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a sulfo group, and a carbon atom number of 1.
-22 alkoxy groups and the like.

As the alkoxy group, a linear or branched alkoxy group having 1 to 22 carbon atoms is preferable, and examples thereof include a methoxy group, an ethoxy group, a 1-propyloxy group, an octyloxy group, a dodecyloxy group, and the like. These alkoxy groups may have a substituent.

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

Similarly, regarding sulfamoyl groups, unsubstituted alkylsulfamoyl groups such as ethylsulfamoyl group, diethylsulfamoyl group, dodecylsulfamoyl group, )'7
Examples include substituted alkylsulfamoyl groups such as 'siloxypropylsulfamoyl group, substituted or unsubstituted arylsulfamoyl groups such as phenylsulfamoyl group and various substituted phenylsulfamoyl groups.

Examples of the acyl group include acetyl group, benzoyl group,
Butanesulfonyl group, benzenesulfonyl group, etc.; Examples of acetoxy groups include acetoxy group, lauroyloxy group, butanesulfonyloxy group, etc.; Examples of alkoxycarbonyl groups include ethoxycarbonyl group, ■-propyloxycarbonyl group, and 2-ethyl group. Examples include xyloxycarbonyl group.

The -NHCOR3 group represents an alkylamide group having 1 to 22 carbon atoms, and representative examples of the unsubstituted alkylamide group include an acetamide group, a butanamide group, a laurylamide group, a stearylamide group, and the like. Further, the alkylamide group may be an alicyclic amide group such as a cyclohexanecarbonamide group, an alkylamide group having a branched structure such as a 2-ethylhexaneamide group, or an alkylamide group containing an unsaturated bond. It may also be an alkylamide group. Typical examples of substituted alkylamide groups include monochloroacetamide groups, trichloroacetamide groups, perfluorobutanamide groups, and other substituted alkylamide groups;
m-pentadecylphenoxyacetamide group, a-(2
, 4-di-t-amylphenoxy)pentanamide group,
Examples include phenoxy-substituted acetamide groups such as α-(2,4-di-t-amylphenoxy)acetamide group and 0-chlorophenoxymyristic acid amide group.

In addition, the -NHCOR, group represents an arylamide group, and representative examples of the unsubstituted arylamide group include benzamide group, naphthamide group, etc., and representative examples of the substituted arylamide group include pt-butylbenzamide group, etc. Amide group, alkyl-substituted benzamide group such as p-methylbenzamide group, p
- Alkoxy-substituted benzamide groups such as methoxybenzamide group and 0-dotesyloxybenzamide group, amide substitution such as p-acetamidobenzamide group, m-(2,4-di-t-aminophenoxyacetamido)penzamide group, etc. Examples include sulfonamide-substituted benzamide groups such as a benzamide group, an 0-hexadecanesulfonamide benzamide group, and a p-butanesulfonamide benzamide group.

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

Moreover, -NHCOOR, represents an aryloxycarbonylamino group, and a typical example thereof is a phenoxycarbonylamino group.

Typical examples include dimethylaminocarbonylamino group, diethylaminocarbonylamino group, and the like.

NHSOxRs represents an alkylsulfonamide group or an arylsulfonamide group, and examples of the alkylsulfonamide group include a methanesulfonamide group, a butanesulfonamide group, a dodecanesulfonamide group, etc. with a carbon atom number of ~
22 unsubstituted alkylsulfonamide groups, substituted alkylsulfonamide groups such as benzylsulfonamide groups, and the like.

Examples of the arylsulfonamide group include an unsubstituted arylsulfonamide group such as a benzenesulfonamide group and a naphthalenesulfonamide group, or a p-toluenesulfonamide group, a 2,4.6-dotecylbenzenesulfonamide group,
Alkyl-substituted benzenesulfonamide groups such as p-dodecylbenzenesulfonamide groups, p-dodecyloxybenzenesulfonamide groups, and alkoxy such as p-butoxybenzenesulfonamide groups! 10 Substituted arylsulfonamide groups such as benzenesulfonamide groups can be mentioned.

-NHSO,N(' represents a sulfamoylamino group,
Typical examples include dialkylsulfamoylamino groups such as dimethylsulfamoylamino group and dibutylsulfamoylamino group.

At least one of A, B and D may have a ballast group.

The ballast group may be one that immobilizes the coupler to the extent that the coupler does not flow out from the silver halide emulsion layer.
For example, it is an alkyl group, an alkenyl group, or an aryl group having 8 or more carbon atoms, preferably 8 to 50 carbon atoms.

Groups that can be separated by a coupling reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine, bromine, fluorine, etc.), hydroxyl groups, alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy group, sulfonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyloxalyloxy group, alkoxyoxalyloxy group, alkylthio group, mercapto group, arylthio group, heterocyclic thio group,
Examples include an alkoxythiocarbonylthio group, an acylamino group, a substituted amine group, a nitrogen-containing heterocyclic group bonded with a nitrogen atom, a sulfonamide group, an alkyloxycarbonylamino group, an aryloxycarbonylamino group, and a carboxyl group. Among these, halogen atoms are preferred;
Particularly preferred is a chlorine atom.

Among the compounds represented by the general formula [I], those in which A or D is an alkyl group or an aryl group are preferred.

Further, among the substituents represented by B, preferably a cyano group,
Examples include an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbamoyl group, and an arylcarbamoyl group.

Hereinafter, typical specific examples of cyan couplers represented by the general formula [I] will be shown, and in the present invention, typical synthetic examples of m = = C force will be shown below.

Synthesis Example 1 5.8 g of ethyl acetoacetate and 5.95 g of ethyl cyanacetate were mixed, and 8.1 g of 70% ethylamine aqueous solution was mixed.
5 g was gradually added, and the mixture was stirred at room temperature until the exotherm stopped.

Thereafter, the mixture was heated and stirred at 90 to 110°C for 2 hours. After cooling, 40IiI2 of water was added and 6.5μα of hydrochloric acid was added dropwise to precipitate white crystals. After filtering the crystals and washing with water,
After drying, 5.15 g of the target product was obtained.

Synthesis Example 2 (Exemplary Coupler 2) 3 g of the compound synthesized in Synthesis Example 1 was added to 100 m of chloroform.
Dissolved in ff, N-chlorosuccinimide (NC5) 1
g was added thereto, and the mixture was stirred at room temperature for 15 hours.

After distilling off the solvent, ethyl acetate and water were added and washed, and the organic layer was dried over magnesium sulfate.

The solvent was distilled off and the product was purified using a silica gel column to obtain the desired product. Yield: 2.1g.

Synthesis Example 3 Mix 5.4 g of ethyl acetoacetate and 5.9 g of ethyl cyanacetate, and add 8.1 g of 70% aqueous dodecylamine solution.
5 g was gradually added, and the mixture was stirred at room temperature until the heat generation stopped.

Thereafter, the mixture was heated and stirred at 90 to 110°C for 2 hours. After cooling, 40vsQ of water was added, and 6.5+++ (2) of hydrochloric acid was added dropwise to precipitate white crystals.

The crystals were collected by filtration, washed with water, and then dried to obtain 5.1 g of the desired product.

Synthesis Example 4 (Exemplary Coupler 5) 3 g of the compound synthesized in Synthesis Example 3 was added to 100 m of chloroform.
Dissolved in ρ, N-chlorosuccinimide (NC3) Ig
was added and stirred at room temperature for 15 hours.

After distilling off the solvent, ethyl acetate and water were added and washed, and the organic layer was dried over magnesium sulfate.

The solvent was distilled off and purified using a silica gel column to obtain the desired product 2.3.
I got g.

In the above synthesis example, the structure of each product was confirmed by NMR and Mass spectrum.

The couplers of this invention typically contain 2
X 10-' to 8 X 10-' moles, preferably 1×
It can be used in the range of 101 to 5 x 10-' moles.

The couplers of the present invention can be used in combination of two or more types, or can be used in combination with other types of cyan couplers.

The coupler of the present invention can be produced by solid dispersion method, latex dispersion method,
It can be added to silver halide photographic materials using various methods such as oil-in-ice emulsion dispersion method. For example, in the oil-in-water emulsion dispersion method, hydrophobic additives such as couplers are usually
Gelatin is dissolved in a high boiling point organic solvent with a boiling point of about 150°C or higher, such as tricresyl phosphate or dibutyl phthalate, in combination with a low boiling point and/or water-soluble organic solvent such as ethyl acetate or butyl propionate, if necessary. It may be emulsified and dispersed in a hydrophilic binder such as an aqueous solution using a surfactant, and then added to the desired hydrophilic colloid layer.

The silver halide photographic light-sensitive material of the present invention can be applied to, for example, color negative, positive and reversal films, and color photographic paper, but the present invention is especially suitable when applied to color photographic paper used for direct viewing. The effect is effectively demonstrated.

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

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

Silver halide emulsions can be chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization, and the like. or,
Optical sensitization can be achieved to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry.

The silver halide photographic light-sensitive material of the present invention includes a color anti-capri agent, a hardening agent, a plasticizer, a polymer latex, an ultraviolet absorber, a formalin scavenger mordant, a development accelerator, a development retardant, a fluorescent brightener, Matting agents, lubricants, antistatic agents,
Surfactants and the like can be optionally used.

In the present invention, any treatment used in the art may be performed, such as color development treatment, bleaching, fixing, bleach-fixing, stabilization, washing with water, and stopping.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 The following comparative coupler (A) was heated and dissolved with 1/2 weight of dioctyl phthalate and 3 times the amount of ethyl acetate,
It is emulsified and dispersed in a 5% gelatin solution to which Alkanol xC (manufactured by DuPont) is added as a surfactant. This dispersion was mixed with a silver chlorobromide emulsion (silver bromide 80 mol%) so that the coupler was 0.35 mol per mol of silver, applied to a paper support laminated on both sides with polyethylene, and dried. Sample 1 was obtained. (Amount of coupler applied 1.2X 10-'
Mol/1100a”, coated silver amount 3.7mg/100
Samples 2 to 4 were obtained in the same manner as Sample 1, except that the couplers in Sample 1 were replaced with the couplers shown in Table 1.

However, for the 4-equivalent coupler, the amount of silver coated was doubled.

The sample obtained above was exposed to light through an optical wedge according to a conventional method, and then processed in the following steps.

Processing process Processing temperature Processing time Color development
Bleach and fix at 33°C for 3 minutes and 30 seconds at 33°O
Wash with water for 1 minute and 30 seconds at 33℃
Dry for 3 minutes 50-80°C2
The composition of each treatment solution is as follows.

Color developer Benzyl alcohol 12+ff Diethylene glycol 10 Q Potassium subacid 25 g Sodium bromide 0.6 g Anhydrous sodium sulfite 2.0 g Hydroxylamine sulfate 2.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4 - Add 4.5 g of aminoaniline sulfate water to make If, and adjust to pull with sodium hydroxide.

Bleach-fixing solution Ammonium thiosulfate 120g Sodium metabisulfite 15g Anhydrous sodium sulfite 3g Ethylenediaminetetraacetic acid ferric ammonium salt 65g Add water to make 112 and adjust pH to 6.7-6.8.

Sensitometry was measured for Samples 1 to 4 treated above using a densitometer (Konica Corporation Model KD-7R). Relative sensitivity is a relative value with sample 1 set as 100. Dm
ax (maximum density) was measured using transmitted light.

Further, the dye image of each sample obtained in this manner was used to measure the reflection spectrum at a reflection density of 1.0 using a self-recording spectrophotometer (Model 320, Hitachi Ltd.) equipped with an integrating sphere. (
The reference side is magnesium oxide) Table 1 Comparative coupler (A) It can be seen that it is color-forming and has sharp spectral absorption characteristics.

〔Effect of the invention〕

The silver halide photographic light-sensitive material of the present invention has good spectral absorption characteristics of the cyan dye formed, that is, it has good sharpness on the short wavelength side, has little irregular absorption in the green part and the blue part, and has good color reproducibility. Are better. Furthermore, since the density of cyan dye generated is high, that is, the cyan coupler of the present invention has high coloring properties, it is possible to improve sharpness by making the film thinner.

[Brief explanation of the drawing]

FIG. 1 shows an exemplary coupler 5 of the present invention and a comparative coupler (A
) is a spectral absorption curve of cyan dye obtained from

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula [I]. A silver halide photographic material containing the cyan coupler shown below. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, A, B, and D each represent a substituent bonded to the pyridone ring via a carbon atom, nitrogen atom, oxygen atom, or sulfur atom. A, B and D may be the same or different. X represents a hydrogen atom or a group capable of being eliminated by a coupling reaction with an oxidized product of a color developing agent. ]