JPH0365528B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention can be used in photographic technology, particularly in improving photographic light-sensitive materials. The present invention relates to a novel cyan dye image-forming coupler and a silver halide photographic material containing the above coupler. Prior Art Conventional silver halide color photographic images are produced by three different processes in which an aromatic primary amine color developing agent oxidizes itself when it reduces exposed silver halide grains, forming dyes. It is obtained by a coupling reaction between a coupler and a silver halide emulsion. In the above method, color reproduction is performed by a subtractive color method, and three colors, yellow, magenta, and cyan, are used. Among these, couplers widely used to form cyan dyes are phenols and naphthols. In particular, what is desired to be improved in the phenolic cyan coupler used as the final image is that the cyan dye formed first has good spectral absorption characteristics, that is, in the green region of the absorption spectrum (particularly in the 500 nm to 550 nm range). ) absorption is small and the maximum absorption wavelength is long wavelength (640nm to 660nm)
m), the second cyan dye formed has sufficient fastness to light, heat, and moisture, and there is little contamination in the uncolored area under such storage conditions. Thirdly, it has good coloring properties, that is, it has sufficient coloring sensitivity and coloring density.Fourthly, bleaching baths or bleach-fixing baths containing EDTA ferric salt as a main component have a long-term durability. There is no loss of pigment even after fatigue due to use. In order to improve these drawbacks, many techniques have been published. Especially the 4th one above.
A 2,5-diacylaminophenol coupler is attracting attention because of its excellent properties against dots. For example, couplers having acylamino groups at the 2- and 5-positions of phenol are described in US Pat. No. 2,772,162 and US Pat. No. 2,895,826. Although these couplers do have excellent cyan dye heat resistance and excellent spectral absorption characteristics, they have serious drawbacks in that the coloring properties of the couplers themselves and the light resistance of the dyes are extremely poor. Therefore, in order to improve these drawbacks, a so-called two-equivalent type coupler, in which a fluorine atom is introduced at the 4-position of the phenol nucleus that performs a coupling reaction with the oxidized form of a color developing agent, was disclosed, for example, in U.S. Pat. No. 3,758,308, and has excellent properties. Although these couplers exhibited color-forming properties, they had the undesirable property of causing yellow staining when exposed to light. In addition, 2,5-diacylaminophenol couplers having a pentafluorobenzamide group at the 2-position of the phenol nucleus are disclosed in U.S. Pat.
Described in No. 3880661. Furthermore, a cyan coupler in which an O-sulfonamide benzamide group is introduced at the 2-position of the phenol nucleus is described in JP-A-56-80045. The couplers described in these publications are satisfactory with respect to spectral absorption properties, but are not always sufficient with respect to dye fastness. In addition, 2,5-diacylaminophenol cyan couplers having a sulfonamide group at the 5-position of the phenol nucleus have been developed.
No. 109630, No. 55-163537, No. 56-29235, No. 56-29235, No.
No. 56-99341, No. 56-116030, No. 56-55945, and No. 56-80054. Furthermore, the 2,5-
Diacylaminophenol coupler was published in Japanese Patent Publication No. 1986-
Described in No. 161542. Dyes produced from these couplers have excellent fastness, but have poor spectral absorption properties. OBJECTS OF THE INVENTION It is an object of the present invention to provide a phenolic cyan coupler which improves the above-mentioned drawbacks, has excellent spectral absorption, and has improved color staining and image storage stability, and also has other objects. The object of the present invention is to provide a silver halide photographic material containing a phenolic cyan coupler which is excellent in spectral absorption characteristics, color staining, and image storage stability. According to the present invention, the above object is achieved by a phenolic cyan coupler having a substituent represented by the following general formula [] at the 2-position of the phenol nucleus and an acylamino group at the 5-position of the phenol nucleus. I found out what I can do. general formula In the formula, R ¹ represents a halogen atom or a monovalent organic group. n represents an integer of 0 to 3, and when n is 2 or more, R ¹ may be the same or different. The present invention will be explained in more detail below. The phenolic cyan coupler of the present invention is characterized by having a group represented by the above general formula [] at the 2-position of the phenol nucleus and an acylamino group at the 5-position. In the present invention, R ¹ in the group represented by the general formula [] represents a halogen atom or a monovalent organic group as described above, and examples of the halogen atom include fluorine, chlorine, bromine, iodine, etc. Examples of the monovalent organic group represented by R ¹ include nitro group, amino group,
cyano group, hydroxyl group, carboxyl group, alkyl group having 1 to 20 carbon atoms (e.g. methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, octyl group, benzyl group, phenethyl group, etc.),
Alkoxy group (e.g. methoxy group, ethoxy group,
benzyloxy group, etc.), aryloxy group (e.g., phenoxy group, P-nitrophenoxy group, etc.),
Acylamino group (e.g. acetylamino group, propionylamino group, benzoylamino group, phenoxyacetylamino group, etc.), carbamoyl group (e.g. methylcarbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, diphenylcarbamoyl group, etc.), sulfone Amide group (e.g. methanesulfonamide group, butanesulfonamide group,
benzenesulfonamide group, P-toluenesulfonamide group, etc.), sulfamoyl group (e.g. methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), alkylcarbonyl group (e.g. methylcarbonyl group, propyl carbonyl group, octylcarbonyl group, etc.),
Arylcarbonyl group (e.g. phenylcarbonyl group, etc.), alkyloxycarbonyl group (e.g. methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, t-butyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g. phenyloxycarbonyl group, etc.) (oxycarbonyl group, methoxyphenyloxycarbonyl group, etc.), alkylsulfonyl groups (eg, methanesulfonyl group, butanesulfonyl group, etc.), arylsulfonyl groups (eg, benzenesulfonyl group, etc.), and the like. In the present invention, the phenolic cyan coupler having a substituent represented by the above general formula [] at the 2-position of the phenol nucleus and an acylamino group at the 5-position can preferably be represented by the following general formula []. General formula [] In the formula, R ¹ represents a group having the same meaning as R ¹ in the above general formula [], n represents an integer of 0 to 3, and n
is 2 or more, R ¹ may be the same or different, and R ² represents a ballast group, specifically preferably a linear or branched alkyl group having 4 to 30 carbon atoms (for example, (t-butyl group, n-octyl group, t-octyl group, n-dodecyl group, etc.), alkenyl group, alkoxyalkyl group, or cycloalkyl group, 5- or 6-membered heterocyclic group,
Or it represents a group represented by the following general formula []. General formula [] In the formula, J represents an oxygen atom or a sulfur atom, and R ³ represents a linear or branched alkylene group having 1 to 20 carbon atoms. This alkylene group is preferably a methylene group, a 1,1-ethylene group, a 1,2-
Ethylene group, 2,2-propylene group, 1,3-propylene group, 1,1-isobutylene group, 1,1-
Examples include a bentylene group, a 3-methyl-1,1-butylene group, a 1,1-hebutylene group, a 1,1-nonylene group, a 1,1-dodecylene group, and a 1,1-tridecylene group. and R ⁴ is a halogen atom (preferably chlorine or bromine), an alkyl group {preferably a straight chain or branched chain having 1 to 20 carbon atoms;
alkyl groups (e.g. methyl, tert-butyl,
tert-pentyl, tert-octyl, dodecyl, pentadecyl, benzyl, phenethyl)}, aryl groups (e.g. phenyl), heterocyclic groups (preferably,
hydrogen-containing heterocyclic group), alkoxy group {preferably,
Straight-chain or branched alkyloxy groups having 1 to 20 carbon atoms (e.g., methoxy, ethoxy, tert-butyloxy, octyloxy, decyloxy, dodecyloxy)}, aryloxy groups (e.g., phenoxy), hydroxyl groups, acyloxy groups { Preferably an alkylcarbonyloxy group, an arylcarbonyloxy group (e.g. acetoxy, benzoyloxy)}, a carboxy group, an alkoxycarbonyl group (preferably a linear or branched alkyloxycarbonyl having 1 to 20 carbon atoms), an aryloxycarbonyl group (preferably phonoxycarbonyl), mercapto group, alkylthio group {preferably a linear or branched alkylthio group having 1 to 20 carbon atoms (e.g. methylthio, octylthio, dodecylthio)}, acyl group (preferably having 1 to 20 carbon atoms) straight-chain or branched alkylcarbonyl), acylamino group (preferably straight-chain or branched alkylcarboxamide with 1 to 20 carbon atoms, benzenecarboxamide), sulfonamide group (preferably with 1 to 20 carbon atoms)
20 linear or branched alkylsulfonamide group, benzenesulfonamide group), carbamoyl group (preferably alkylaminocarbonyl or phenylaminocarbonyl having 1 to 20 carbon atoms), sulfamoyl group (preferably 1 to 20 carbon atoms) m represents an integer of 0 to 4, and 1 represents an integer of 0 or 1. Typical specific examples of the coupler of the present invention represented by the above general formula are described below, but the present invention is not limited thereto. The phenolic cyan coupler represented by the general formula [] exemplified above can be synthesized, for example, according to the following reaction steps. Next, a specific method for synthesizing the phenolic cyan coupler of the present invention will be described. Synthesis Example 1 Synthesis method of exemplified coupler (1) [2-(2,3,5,6-tetrafluoro-4-
pyridine carboxide)-4-chloro-5-{α-
Synthesis of 2,4-di-t-amylphenoxy)iso-valeramide-}phenol Step 1 18.9 g (0.10 mol) of 2-amino-4-chloro-5-nitrophenol was dispersed in 100 ml of acetonitrile, and 21.4 g (0.10 mol) of 2,3,
A solution of 25 ml of 5,6 tetrafluoro-4-pyridinecarboxylic acid chloride in acetonitrile was added dropwise.
After heating and refluxing for 2 hours, the reaction solution was ice-cooled, and the precipitated solid was collected by filtration, washed with cooled acetonitrile, and dried to give 2-(2,3,5,6-tetrafluoro-
4-pyridinecarboxide)-4-chloro-5
-29 g of nitrophenol (yield 79%) was obtained. Step 2 Dissolve 20 g (0.055 mol) of the above crude crystals in 600 ml of alcohol, add palladium-carbon catalyst,
Catalytic reduction with hydrogen gas was performed at room temperature and pressure. After introducing a molar equivalent of hydrogen gas, the palladium-carbon catalyst was filtered off and the filtrate was concentrated. The residue was dissolved in acetonitrile and then recrystallized to obtain 16 g of 2-(2,3,5,6-tetrafluoro-4-pyridine carboxide)-4-chloro-5-aminophenol. (Yield 87%) Step 3 12 g (0.036 mol) of the above phenol derivative and
14.1 g (0.040 mol) of α-(2,4-di-t-amylphenoxy)iso-valeroyl chloride
Dissolve in 150ml of tetrahydrofuran and cool on ice for 5 minutes.
g (0.064 mol) of pyridine was slowly added dropwise.
After stirring at room temperature for 20 hours, the solvent was distilled off under reduced pressure.
The residue was dissolved in a mixed solvent of acetonitrile and ethanol.
Recrystallization was performed from 110 ml to obtain 12 g (yield 51%) of the target compound, exemplified coupler (1). Melting point 180°~184°C,
The structure was confirmed by mass spectroscopy, elemental analysis, proton NMR spectrum, etc. Synthesis Example 2 Synthesis method of exemplified coupler (6) [2-(2,3,5,6-tetrafluoro-4-
pyridine carboxide)-4-chloro-5-{α-
Synthesis of (4-dimethylaminosulfonylaminophenoxy)tetradecanamide}phenol] Intermediate 2- obtained in Step 2 of Synthesis Example (1) above
(2,3,5,6-tetrafluoro-4-pyridinecarboxide)-4-chloro-5-aminophenol 10 g (0.030 mol) and 16.2 g (0.035 mol)
of α-(4-dimethylaminosulfonylaminophenoxy)tetradecanoic acid chloride was suspended in 100 ml of acetic acid, and 5.0 g (0.060 mol) of sodium acetate was added. After stirring at room temperature for 2 hours, the anti-mixture was poured into 100 ml of water, the solution was made acidic with hydrochloric acid, and the solid was collected by filtration. This was recrystallized from acetonitrile. Exemplary coupler (6) 10.3g (yield 45
%) was obtained. Melting point 152-155℃, mass spectrum,
The structure was confirmed by elemental analysis and proton NMR spectrum. The thus obtained silver halide photographic material containing the phenolic cyan coupler of the present invention not only has excellent sensitivity, color density, and color reproducibility, but also has higher dye light resistance than conventional couplers. It has excellent properties such as hardness, heat resistance and moisture resistance, prevents staining, and has good image properties. In order to incorporate the phenolic cyan coupler of the present invention into a silver halide emulsion, a conventionally known method may be followed. For example, the present invention can be applied to a high boiling point organic solvent with a boiling point of 175°C or higher such as tricresyl phosphate and dibutyl phthalate, or a low boiling point organic solvent such as butyl acetate and butyl propionate, either alone or as a mixture thereof as necessary. couplers, alone or in combination, are mixed with an aqueous gelatin solution containing a surfactant, then emulsified in a high-speed rotary mixer, ultrasonic disperser or colloid mill, and then added to the silver halide. Silver halide emulsions used in the present invention can be prepared.
When the coupler of the present invention is added to a silver halide emulsion, the amount usually added is, for example, about 0.07 to 0.7 mol, preferably 0.1 mol per mol of silver halide.
The couplers of the invention are added in amounts ranging from mol to 0.4 mol. The couplers of the present invention may be used alone or in combination, or may be used in combination with other phenolic or naphthol cyan couplers. The silver halide color photographic light-sensitive material containing the phenolic cyan coupler of the present invention (hereinafter referred to as the light-sensitive material according to the present invention) may be a monochrome element or a multicolor element. When used in other color elements, the cyan coupler of the present invention is normally included in red-sensitive emulsions, but may also be included in unsensitized emulsions or emulsion layers sensitive to the three primary color regions of the spectrum other than red-sensitized. You may let them. Each unit of the multicolor element may consist of either a single emulsion layer or multiple emulsion layers sensitive to a certain region of the spectrum. The layers of the element, including the layers of imaging units, can be arranged in various orders as is known in the art. A typical multicolor photographic element is
A cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan coupler (at least one of the cyan couplers being a coupler of the present invention) and at least one red-sensitive silver halide emulsion layer having at least one magenta coupler. A magenta dye image-forming unit consisting of two green-sensitive silver halide emulsion layers and a yellow dye image-forming unit consisting of at least one blue-sensitive silver halide emulsion layer having at least one yellow coupler were carried on a support. consists of things. The silver halide used in the silver halide emulsion of the photosensitive layer in the present invention includes conventional silver halides such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any used is included. The silver halide emulsion constituting the silver halide emulsion layer used in the present invention can be produced by various manufacturing methods including the usual manufacturing method, for example, the method described in Japanese Patent Publication No. 7772/1983, or the method described in U.S. Pat. 2592250, that is, 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 combined with silver bromide or iodine. A method for producing a so-called conversion emulsion, such as converting it into a silver oxide salt,
Alternatively, it can be produced by any production method such as the Lipman emulsion production method consisting of fine-grained silver halide having an average grain size of 0.1 μm or less. Furthermore, the above silver halide emulsion 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 metal sensitizers, such as gold sensitizers, specifically potassium aurithioxyanate, olium chloroaurate, 2-ourosulfobenzthiazole methyl chloride, etc., or water-soluble salts such as ruthenium, rhodium, iridium, etc. Chemical sensitization can be carried out using a sensitizer, specifically ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadide, etc. alone or in combination as appropriate. Further, the above-mentioned silver halide emulsion can contain various known photographic additives. For example, research disclosure
Disclosure) Photographic additives such as those described in December 1978 Item 17643. In the photosensitive material of the present invention, hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein,
Any of cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide are included. The photosensitive material of the present invention may be subjected to corona discharge treatment, fire treatment or ultraviolet irradiation treatment along with the emulsion layer of the present invention containing the various photographic additives as described above, as required. It can be produced by coating on a coated support, or by coating it on a support via a subbing layer or an intermediate layer. Advantageously used supports include, for example, Paraita paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or with a reflective material,
Examples include glass plates, polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and these supports are appropriately selected depending on the intended use of the photosensitive material. Various coating methods such as dipping coating, air doctor coating, curtain coating, and popper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also, U.S. Patent No.
2 by the method described in No. 2761791 and No. 2941898
Simultaneous application of more than one layer can also be used. In addition, in the sensitive material according to the present invention, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and furthermore, a filter layer, an anti-curl layer, a protective layer,
Various layers such as antihalation layers can be used in appropriate combinations as constituent layers. Hydrophilic colloids that can be used in the emulsion as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included as well. The photosensitive material according to the present invention is used for various purposes, and exhibits excellent properties depending on the purpose. Although it can be used as a photosensitive material (for high resolution), it is particularly suitable as color printing paper. The silver halide used in the present invention imparts photosensitivity to the wavelength range required for red-sensitive emulsions.
Spectral sensitization is achieved by selection of appropriate sensitizing dyes. 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, US Pat. No. 2,269,233
No. 2270387, No. 2442710, No. 2442710, No. 2270387, No. 2442710, No.
Typical examples include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in the specifications of No. 2454629 and No. 2776280. The color developing solution that can be used in the present invention preferably has an aromatic primary amine color developing agent as a main component. Typical examples of this color developing agent include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, and dimethyl-p-phenylenediamine hydrochloride. Diamine hydrochloride, 2-amino-5-dimethylaminotoluene 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-amino-5-
(N-ethyl-N-β-methoxyethyl)aminotoluene and the like. These color developing agents may be used alone or in combination of two or more, and if necessary, may be used in combination with black and white developing agents such as hydroquinone and phenidone. In addition, the color developing solution containing the above-mentioned developing agent is generally an alkaline agent such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfate,
It contains sodium sulfite, etc., and may also contain various additives, such as alkali metal halides (potassium bromide, etc.), or development regulators, such as citradinic acid. EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. Example 1 Using the phenolic cyan coupler of the present invention and the comparative coupler shown in Table 1 below, 10 g of each was added to a mixed solution of 5 ml of di-n-butyl phthalate and 30 ml of ethyl acetate, and the mixture was heated to 60°C. It was completely dissolved. This solution was added to Alkanol B (alkylnaphthalene sulfonate, manufactured by Dupont).
5 ml of 10% aqueous solution and 200 ml of 5% gelatin aqueous solution
ml and emulsified using a colloid mill to prepare respective coupler dispersions. Next, this coupler dispersion was added to 500 g of gelatin silver chlorobromide emulsion, coated on polyethylene-coated paper, and dried to prepare a total of six types of silver halide color photographic light-sensitive materials. These samples were subjected to wedge exposure according to a conventional method and then processed as follows. Processing step (30°C) Processing time Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Water washing 2 minutes The composition of each processing solution is shown below. [Color developer composition] 4-amino-3-methyl-N-ethyl-N-
(β-Methanesulfonamidoethyl)-aniline sulfate 5.0g Benzyl alcohol 15.0ml 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, then water Adjust the pH to 10.30 using sodium oxide. [Bleach-fix solution composition] Ethylenediaminetetraacetate iron amnium salt
61.0g Ethylenediaminetetraacetate iron diammonium salt 5.0g Ammonium thiosulfate 124.5g Sodium metabisulfite 13.3g Anhydrous sodium sulfite 2.7g Add water to make 1. The photographic properties of each sample obtained by the above treatment were measured. In addition, when measuring
A PDA-60 type densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) was used. The results obtained are shown in Table 1 below. The sensitivity values in the table are the values of the sample with the maximum sensitivity.
Relative sensitivity was expressed as 100.

【table】

[Table] As is clear from the above table, Samples 5 and 6 using comparative couplers have problems especially in sensitivity, maximum density, and spectral absorption characteristics, but all samples using couplers of the present invention have problems in sensitivity, maximum density, and spectral absorption characteristics. It was found that the coupler of the present invention exhibits excellent performance in terms of maximum density and spectral absorption characteristics, and is a coupler with good coloring properties. Example 2 A sample having a cyan dye image was prepared in exactly the same manner as in Example 1 using the phenolic cyan coupler of the present invention and a comparative coupler as shown in Table 2 below. Using this sample, experiments and studies were conducted on the light resistance, heat resistance, moisture resistance, and staining of the dye. The results obtained are listed in Table 2 below. In the table, light resistance is measured after exposing each dye image to a xenon fade meter for 200 hours, heat resistance is after storage at 77℃ for 2 weeks, and humidity resistance is after storage at 60℃ and 80% relative humidity for 2 weeks. The residual rate after each initial concentration of 1.0 is expressed as a percentage. In addition, stain is expressed as a percentage increase in blue density in the unexposed area of the sample subjected to the light resistance test.

【table】

[Table] As is clear from the results in the table above, the first
Comparative coupler (A) with good color development in the table
has significantly poor heat resistance and moisture resistance, comparative couplers (C) and (D) have problems with light resistance, and comparative coupler (E) has a large amount of staining, so all comparative couplers leave room for improvement. It was full of stuff. On the other hand, as shown in Table 1, the coupler of the present invention not only has excellent sensitivity and image quality, but also has excellent physical properties, that is, image preservation and stability. I found out something. Effects of the Invention The phenolic cyan coupler of the present invention not only has excellent sensitivity, color density, and color reproducibility, but also has excellent light resistance, heat resistance, and moisture resistance, and can obtain color images without staining. I can do it.

Claims (1)

[Scope of Claims] 1. Having a substituent represented by the following general formula [] at the 2-position of the phenol nucleus, and 5 of the phenol nucleus.
A phenolic cyan coupler characterized by having an acylamino group at the position. General formula [] (In the formula, R ¹ represents a halogen atom or a monovalent organic group. n represents an integer of 0 to 3, and when n is 2 or more, R ¹ may be the same or different.)