JPS6310819B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material suitable particularly as a printing material. Prior art and its problems Color photographic images using silver halide are produced by the aromatic primary amine color developing agent itself being oxidized when reducing exposed silver halide grains and reacting with this oxidized product. A dye image is obtained by reacting three different dye-forming couplers in a silver halide emulsion to form a dye image. In this method, color reproduction is performed by a subtractive color method, and three colors, yellow, magenta, and cyan, have been used. Couplers commonly used to form cyan dyes are phenols and naphthols. In particular, what is desired to be improved in a phenolic cyan coupler suitable as a sensitive material for printing is that the cyan dye formed first has good spectral absorption characteristics, that is, the green region of the absorption spectrum (particularly 500 to 550 nm), and the maximum absorption wavelength is long wavelength (640 to 550 nm).
660nm). Second, the cyan dye formed has sufficient fastness to light, heat, and moisture. Thirdly, it has good color development. In other words, it must have sufficient color development sensitivity and color density.
Fourthly, a bleaching bath mainly composed of EDTA ferric salt;
Or, there is no loss of dye even when the bleach-fix bath is fatigued by running. Many techniques have been published to date to improve these points. In particular, 2,5-diacylaminophenol cyan coupler is a cyan coupler that has attracted attention because of its excellent fourth point. This is for example US Patent No. 2,772,162;
Described in No. 2895826. However, although these cyan dyes have excellent heat resistance and excellent spectral properties, they have serious drawbacks in that the couplers have poor coloring properties and the dyes have extremely poor light resistance. In order to improve these drawbacks, couplers in which a fluorine atom is substituted at the 4-position of the phenol are described in U.S. Pat. It tends to occur easily and has undesirable properties. In addition, 2,5-diacylaminophenol couplers having a pentafluorobenzamide group at the 2-position of the phenol are disclosed in U.S. Pat.
Described in No. 3880661. However, the couplers described in these patent documents cannot be said to be sufficient in terms of dye fastness. Furthermore, 2,5-diacylaminophenolic cyan couplers having a sulfonamide group at the 5-position of the phenol have been developed. For example, Tokukai Akira
53-109630, 56-29235, 55-163537, 56
-99341, 56-116030, 56-55945, 56-
There are 80045 etc. However, these couplers also have good robustness but poor spectral properties. As described above, conventional cyan couplers have not yet been implemented that can satisfy all of the conditions, and in recent years, there has been a strong desire for cyan couplers that satisfy these various characteristics. OBJECTS OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic material containing a cyan coupler that satisfies all of the above-mentioned first to fourth required characteristics. It has been found that this purpose can be achieved as follows. In other words, as a cyan coupler,
It has been found that this can be achieved by a silver halide color photographic light-sensitive material characterized by containing a compound represented by the following general formula []. General formula [] Here, R ¹ represents a branched or straight chain alkylene group, R ² represents an alkylsulfonamide group,
Represents a phenyl group having an arylsulfonamide group or an aminosulfonamide group. Specific Structure of the Invention In the above general formula [], R ¹ represents a branched or straight chain alkylene group. In this case, the alkylene group preferably has 1 to 20 carbon atoms. On the other hand, R ² represents a phenyl group substituted with at least one of an alkylsulfonamide group, an arylsulfonamide group, and an aminosulfonamide group. Next, specific representative examples of the compound represented by the general formula [] in the present invention will be shown, but the present invention is not limited thereto. Specific compound examples These compounds represented by the general formula [] are:
It can be synthesized according to the following reaction formula. In addition, R represents ^R2 -O- ^R1- . Next, a specific synthesis example of the compound represented by the general formula [] will be shown. Synthesis Example 1 Coupler (1): 2-(2,3,4,5,6-pentafluorobenzamide)-4-chloro-5-
{α-(4-dimethylaminosulfonylaminophenoxy)tetradecanamide}phenol (A) Disperse 18.9 g (0.10 mole) of 2-amino-4-chloro-5-nitrophenol in 100 ml of acetonitrile, and make 23.1 g of it. (0.10mole) 2,
A solution of 3,4,5,6-pentafluorobenzoic acid chloride in 50 ml of acetone was added dropwise. After heating under reflux for 3 hours, the reaction solution was cooled with water, the precipitated solid was collected, and after washing with cooled acetonitrile,
After drying, 32.5 g (yield: 85%) of 2-(2,3,4,5,6-pentafluorobenzamide)-4-chloro-5-nitrophenol was obtained. (b) 16 g (0.042 mole) of the above crude crystals were dissolved in 500 ml of alcohol, a palladium-carbon catalyst was added, and catalytic reduction with hydrogen was performed at room temperature and pressure. Next, separate the palladium-carbon catalyst,
The liquid was concentrated. The residue was dissolved in 200 ml of acetonitrile and recrystallized to give 11 g of 2-(2,3,4,5,
6-pentafluorobenzamide)-4-chloro-5-aminophenol was obtained. (Yield 74%) (c) Dissolve 10 g (0.028 mole) of the above phenol derivative and 13.8 g (0.030 mole) α-(4-dimethylaminosulfonylaminophenoxy)tetradecanoic acid chloride in 150 ml of tetrahydrofuran, and place on ice. While cooling, 4 g (0.050 mole) of pyridine was slowly added dropwise. After stirring at room temperature for 2 hours, the solvent was distilled off under reduced pressure. The residue was recrystallized from 200 ml of a 1:1 mixed solvent of n-hexane and ethyl acetate to obtain 12.4 g (yield 53%) of target coupler No.
I got 1. mp130-131℃ Confirmation of the structure of the target product using mass spectra, elemental analysis, and proton analysis.
This was done by NMR spectroscopy. Synthesis Example 2 Coupler No. 2: 2-(2,3,4,5,6-pentafluorobenzamide)-4-chloro-5
-{α-(4-butanesulfonylaminophenoxy)tetradecanamide}phenol Intermediate 2 (2,3,4,5,6
-pentafluorobenzamide)-4-chloro-
5-aminophenol 10g (0.028mole) and 14.2
g (0.030 mole) of α-(4-butanesulfonylaminophenoxy)tetradecanoic acid chloride.
It was suspended in 100 ml of acetic acid and 3.3 g (0.040 mole) of sodium acetate was added. After stirring at room temperature for 3 hours, add water
Pour into 500 ml and separate the solid. After drying the solids,
Recrystallized from acetonitrile to give 14.2g (yield: 60
%) of the target product was obtained. mp.127-131℃The structure of the target product was confirmed by mass spectrometry, elemental analysis, and proton NMR spectrum, and it was confirmed to be the target product. Such couplers are generally lipophilic, and in order to incorporate them into a sensitive material, at least one compound represented by the general formula [ ] is dissolved in a high boiling point organic solvent as a so-called oil protector to protect against halogens in the sensitive material. It is contained in a silver oxide emulsion layer (generally a red-sensitive emulsion layer or a layer adjacent thereto). In order to incorporate the coupler of the present invention into the emulsion layer of a color sensitive material, a conventionally known method can be used, for example, a high boiling point organic solvent with a boiling point of 175° C. or higher such as tricresyl phosphate or dibutyl phthalate, or butyl acetate.
After dissolving the coupler of the present invention in a low boiling point solvent such as butyl propionate alone or in a mixture thereof as necessary,
The silver halide emulsion used in the present invention can be prepared by mixing it with an aqueous gelatin solution containing a surfactant, then emulsifying it in a high-speed rotary mixer or a colloid mill, and then adding it to silver halide. In this way, when the above-mentioned coupler is contained in the photosensitive layer of a photosensitive material, it has the advantage of improving color staining etc. because it shows no bad interaction with color development and has particularly good reactivity. There is. Furthermore, the dye obtained using the coupler of the present invention satisfies the above-mentioned excellent color absorption properties. The photosensitive layer (silver halide emulsion layer) of the photosensitive material containing the cyan coupler according to the present invention is generally red-sensitive, and the silver halides used include silver bromide, silver chloride, and silver iodobromide. , silver chlorobromide, silver chloroiodobromide, and any other materials used in ordinary silver halide emulsions are included. The silver halide emulsion constituting the silver halide emulsion can be manufactured by the usual manufacturing method,
Various manufacturing methods, such as those described in Japanese Patent Publication No. 46-7772, or U.S. Pat.
No. 2,592,250, ie, forming an emulsion of silver salt grains consisting of at least a portion of a silver salt whose solubility is greater than that of silver bromide, and then at least a portion of the grains being treated with a silver bromide salt or It can be prepared by any manufacturing method such as a so-called compound emulsion manufacturing method such as conversion into silver iodide salt, or a Lippmann emulsion manufacturing method consisting of fine grained silver halide having an average grain size of 0.1 μm or less. In addition, the silver halide emulsions may contain sulfur sensitizers, such as allylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers, such as stannous salts, polyamines, etc., noble metals. Sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-oresulfobenzthiazole methyl chloride, etc., or, for example, ruthenium,
Chemical sensitization can be carried out using water-soluble salt sensitizers such as rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate, and sodium chloroparadide, alone or in combination as appropriate. The silver halide emulsion can also contain various known photographic additives. The silver halide containing the coupler of the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart sensitivity to the wavelength range required for red-sensitive emulsions. Various spectral sensitizing dyes are used, and these may be used alone or in combination of two or more. Spectral sensitizing dyes advantageously used in the present invention include, for example, U.S. Pat.
Cyanine dyes, merocyanine dyes, or complex cyanine dyes as described in the specifications of No. 2269234, No. 2270378, No. 2442710, No. 2454629, and No. 2776280 are listed as representative examples. Can be done. Such red-sensitive emulsion layers are generally provided on a reflective support. Then, it is usually laminated with other known green-sensitive and blue-sensitive emulsion layers according to a known method to form a light-sensitive material. Specific Uses of the Invention The photosensitive material of the present invention is usually exposed to light through a photographic photosensitive material and then developed with a color developing solution. A preferred color developing agent is one containing an aromatic primary amine color developing agent as a main component. A typical example of this expression agent is p-phenylenediamine, such as diethyl-p
-phenylenediamine hydrochloride, monomethyl-p-
Phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N
-ethyl-N-dodecylamino)-toluene, 2
-amino-5-(N-ethyl-N-β-methanesulfonamidoethyl)aminotoluene sulfate, 4
-(N-ethyl-N-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N
-β-hydroxyethylamino)aniline, 2-
Examples include amino-5-(N-ethyl-N-β-methoxyethyl)aminotoluene. These color developing agents may be used alone or in combination of two or more, and if necessary, in combination with a black and white developing agent such as hydroquinone. Furthermore, color developers generally contain alkaline agents such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfate, sodium sulfite, etc., and various additives such as alkali metal halides, such as potassium bromide, or development modifiers. It may also contain agents such as citradinic acid. Next, various known treatments are performed to obtain a color photographic image. Example 1 Using couplers of the present invention and comparative couplers as shown in Table 1, 10 g of each coupler was added to a mixture of 5 ml of dibutyl phthalate and 50 ml of ethyl acetate, and heated to 60°C to completely dissolve. did. This solution was mixed with 5 ml of a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and 200 ml of a 5% aqueous gelatin solution, and emulsified using a colloid mill to prepare a dispersion of each coupler. Then, add 500% of this coupler dispersion.
g of gelatin-silver chlorobromide (containing 20 mol % silver bromide) emulsion, coated on polyethylene-coated paper, and dried to prepare six types of silver halide color photographic materials. These samples were subjected to wedge exposure according to a conventional method, and then subjected to the following processing. Color development process Color development 30°C 3 minutes 30 seconds Bleach fixing 30°C 1 minute 30 seconds Washing 30°C 2 minutes The composition of each processing solution in the color development process is as follows. Color developer composition 4-amino-3-methyl-N-ethyl-N-
(β-Methanesulfonacidoethyl)-aniline sulfate 5g Benzyl alcohol 15ml Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.85g Sodium bromide 1.4g Potassium bromide 0.5g Borax 39.1g Add water to make 1 and sodium hydroxide Adjust the pH to 10.3 using Bleach-fix solution composition Ethylenediaminetetraacetic acid iron ammonium salt
61.0g Ethylenediaminetetraacetic acid diammonium salt
5.0 g Ammonium thiosulfate 124.5 g Sodium metabisulfite 13.5 g Anhydrous sodium sulfite 2.7 g Water was added to make up to 1. Photographic properties were measured for each sample obtained after processing. Incidentally, a PDA-60 type densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) was used for the measurement. The results are shown in Table 1. The sensitivities in the table are expressed as relative sensitivities, with the sensitivity of sample No. 1 set as 100.

[Table] As is clear from Table 1, the sample containing the cyan coupler of the present invention has favorable spectral reflection characteristics and exhibits excellent color development in terms of photographic performance.
It can be seen that it has greater color density and sensitivity than any of the comparative couplers. Example 2 Using the couplers of the present invention and comparative couplers as shown in Table 2, cyan dye images were formed in the same manner as in Example 1. Regarding the samples, light resistance, heat resistance,
We investigated moisture resistance and stain. The results obtained are shown in Table 2.

[Table] In addition, the light resistance in the table is the heat resistance after 200 hours of exposure of each sample obtained with a xenon fade meter.
The humidity resistance after two weeks at 77°C and 80% relative humidity is expressed as the residual rate (%) with respect to the initial concentration of 1.0. In addition, the stain was expressed as the rate of increase in blue density (%) in the unexposed area of the sample subjected to the light resistance test. Measurements were carried out in the same manner as in Example 1. As is clear from Table 2, comparative couplers C and D
Although heat resistance and moisture resistance are not so good, light resistance is extremely poor, and comparison coupler (E) shows good results in light resistance, heat resistance, and moisture resistance compared to other comparison couplers, but staining is considerably large. . However, it can be seen that the cyan coupler of the present invention has very good performance in all aspects.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material containing a compound represented by the following general formula [] as a cyan coupler. General formula [] Here, R ¹ represents a branched or straight chain alkylene group, R ² represents an alkylsulfonamide group,
Represents a phenyl group having an arylsulfonamide group or an aminosulfonamide group.