JPH0241737B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel cyan dye image-forming coupler, and more particularly to a silver halide color photographic light-sensitive material containing the above cyan coupler and having improved photographic properties. In general, in silver halide color photographic light-sensitive materials, exposed silver halide grains are reduced with an aromatic primary amine color developing agent, and the oxidation products of the color developing agent produced at this time are yellow, magenta, and cyan. A color dye image can be obtained by oxidative coupling with a coupler forming each dye in a silver halide emulsion layer. The couplers commonly used to form the cyan dyes are phenols or naphthols. The above phenolic cyan coupler has spectral absorption characteristics, especially the cyan dye formed has small absorption in the green region of the absorption spectrum (500 to 550 nm), and its maximum absorption wavelength is on the longer wavelength side (645 to 660 nm). is good and has excellent color reproducibility, but it is not necessarily sufficient in terms of fastness to light resistance, heat resistance, moisture resistance, etc., or storage stability of dyes, and ferric salt of ethylenediaminetetraacetic acid There is still room for improvement regarding fading or loss of dyes during running treatment with bleaching solutions or bleach-fixing solutions containing as the main component.
Furthermore, it is desirable that the color development properties and color development density are also better. Therefore, research has been carried out to satisfy the above-mentioned requirements, but a cyan coupler that can satisfy all of the above-mentioned required properties has not yet been found. For example, for the fading or loss of dyes that occurs during processing with bleach-fix solutions, 2,5 -Diacylaminophenol cyan couplers have excellent performance in the above points, and are also excellent in terms of dye heat resistance and spectral absorption properties, but are significantly inferior in light resistance and the coupler's own coloring properties. There is. As a type of coupler that has improved these drawbacks, a so-called 2-equivalent type coupler, in which a fluorine atom is introduced instead of hydrogen at the 4-position of the phenol nucleus that performs a coupling reaction with the oxidized product of a color developing agent, has been proposed in US Patent No. 3758308 and showed excellent performance, this two-equivalent type coupler also has undesirable properties, such as being susceptible to yellow staining when exposed to light. In addition, a 2,5-diacylaminophenol cyan coupler in which a pentafluorobenzamide group is introduced into the 2-position of the phenol nucleus is disclosed in U.S. Patent No. 3758308.
Although this coupler has excellent spectral absorption characteristics, it cannot be said that it is necessarily satisfactory in terms of dye fastness, which is another important characteristic. On the other hand, examples of cyan couplers that improve the fastness of the above-mentioned dyes include couplers in which a substituent having a sulfonamide group is introduced into the phenol nucleus, such as JP-A-53-109630, JP-A No. 56-29235, JP-A No. 55
−163537, No. 56-99341, No. 56-116030,
It is known from No. 56-55945. However, these couplers are not always satisfactory. Furthermore, 2, which has an alkyl group substituted with at least one fluorine atom at the 2-position of the phenol nucleus,
5-diacylaminophenol cyan couplers have also been developed and are described, for example, in U.S. Pat. No. 2,895,826, U.S. Pat. Although these couplers have excellent dye fastness, they have problems with spectral absorption characteristics and coupler color development. Therefore, the object of the present invention is to improve the above-mentioned conventional drawbacks, and to provide not only excellent sensitivity, maximum dye density, and color reproducibility, but also excellent light resistance, heat resistance, and moisture resistance, and stain resistance. It is another object of the present invention to provide a phenolic cyan coupler for photographic use in which the occurrence of the above phenomenon is prevented, and another object of the present invention is to provide a silver halide color photographic light-sensitive material containing a phenolic photographic coupler having improved photographic properties as described above. It is about providing. As a result of various studies by the present inventors, the above object is to have a benzoylamino group having a fluorinated alkyloxycarbonyl group or a fluorinated phenyloxycarbonyl group at the 2-position of the phenol nucleus, and 5 It has been found that this can be achieved with a phenolic photographic cyan coupler having an acylamino group in the position. That is, the cyan coupler of the present invention can preferably be represented by the following general formula (). General formula () In the formula, Rf is an alkyl substituted with at least one fluorine atom, preferably having 1 carbon atom.
-6 alkyl (e.g. 2,2,2-trisluoloethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,4,4,5,5-octafluoropentyl) or represents an aryl substituted with at least one fluorine atom (e.g. pentafluorophenyl, fluorophenyl, trifluoromethylphenyl), R ¹ represents an alkyl group or an aryl group, R ² represents a hydrogen atom,
halogen atom or monovalent organic group or
Represents COORf group. Further, Z represents a hydrogen atom or a group that can be eliminated upon coupling with an oxidized product of a color developing agent. n represents an integer from 1 to 4,
When n is 2 or more, R ² may be the same or different groups. The alkyl group represented by R ¹ above may be linear or branched and may further have a substituent. Examples of straight-chain or branched alkyl groups include t-butyl, n-dodecyl, and n-hexadecyl, and examples of alkyl groups having substituents include aralkyl (specifically phenethyl), alkoxyalkyl (specifically n-hexyloxyethyl), aryloxyalkyl (specifically 1
-(2,4-di-t-amylphenoxy)propyl, 3-(2,4,6-trichlorophenoxy)
Mention may be made of tridecyl and 1-(3-butanesulfonylaminophenoxy)nonyl. ) Furthermore, the aryl group represented by R ¹ may be substituted, examples of which include a phenyl group, m-pentadecyl phenyl group, p-lauroylaminophenyl group, and the like. Further, the halogen atom represented by R ² is preferably a fluorine atom or a chlorine atom, and examples of the monovalent organic group include an alkyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. , acyl group, alkoxy group, aryloxy group, cyano, carboxy, alkylsulfonamide group, arylsulfonamide group, and the like. Examples of groups represented by Z that can be eliminated during coupling include halogen atoms (preferably fluorine atoms and chlorine atoms), alkoxy groups, aryloxy groups, heteroyloxy groups, alkylthio groups, arylthio groups, heteroylthio groups, alkyl Sulfonamide group, arylsulfonamide group, acyl group, heteroyl group, arylazo group,
A phosphonyloxy group, etc. can be mentioned. Specific representative examples of the phenolic photographic cyan coupler of the present invention represented by the general formula () will be described below, but the present invention is not limited to these. (Exemplary compound) Typical synthesis steps for the phenolic photographic cyan coupler of the present invention and methods for synthesizing exemplified compounds will be described below. (Typical synthesis process) Synthesis Example 1 (Synthesis of Exemplified Compound 1) (1) Synthesis of m-(2,2,3,3-tetrafluoropropyloxycarbonyl)benzoic acid chloride intermediate, isophthalic acid chloride in 250 ml of ethyl acetate
Dissolve 28.4g and 18.4g of 2,2,3,3-tetrafluoropropanol, and dissolve 16.0g of triethylamine.
A 50 ml solution of ethyl acetate was added dropwise at room temperature, stirring was continued for 30 minutes, white crystals were filtered off, and the mixture was concentrated under reduced pressure to obtain 40 g of the desired product as a colorless liquid. (2) 2-[m-2,2,3,3-tetrafluoropropyloxycarbonyl)benzamide]-
Synthesis of 4-chloro-5-nitrophenol intermediate, 11.3 g of 2-amino-4-chloro-5-nitrophenol and m-(2,
2,3,3-tetrafluoropropyloxycarbonyl)benzoic acid chloride 21g, pyridine
Add 7.9g, stir and reflux for 3 hours. After filtering out insoluble matter, cool and collect the resulting precipitate by filtration, wash with acetonitrile, and dry to obtain the desired product as pale yellow crystals.
Obtain 22.5g. (3) 2-[m-2,2,3,3-tetrafluoropropyloxycarbonyl)benzamide]-
Synthesis of 4-chloro-5-aminophenol hydrochloride intermediate, 2-[m-2,2,3,3
-tetrafluoropropyloxycarbonyl)benzamide] -4-chloro-5-nitrophenol 13.5 g, concentrated hydrochloric acid 15 ml, 5% palladium on carbon 1.5
g is added to carry out catalytic reduction with hydrogen gas under normal pressure. After absorbing the theoretical amount of hydrogen gas, the catalyst was filtered off and concentrated under reduced pressure to obtain 11.3 g of the desired product as an off-white powder. (4) Synthesis of Exemplified Compound 1 In 100 ml of acetonitrile, dissolve 5.0 g of the amino hydrochloride obtained in step (3) above and 5.0 g of α-(4-dimethylaminosulfonamidophenoxy)tetradecanoyl chloride, Stir and reflux for 3 hours. After concentrating the reaction solution under reduced pressure, it is added to 300 ml of water and extracted with 500 ml of ethyl acetate. After washing with water and dehydrating with anhydrous magnesium sulfate, concentrate under reduced pressure. The resulting residue is separated and purified by column chromatography using a mixed solution of toluene and acetone as an eluent to obtain 2.08 g of the target product in the form of white crystals. The structure of the above target product was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry. Synthesis Example 2 (Synthesis of Exemplified Compound 12) (1) Synthesis of p-(pentafluorophenyloxycarbonyl)benzoic acid chloride intermediate, Terephthalic acid chloride in 250 ml of ethyl acetate
20.0 g of triethylamine and 25.8 g of pentafluorophenol were dissolved, and a solution of 15.0 g of triethylamine in 50 ml of ethyl acetate was added dropwise at room temperature. After stirring for 30 minutes, insoluble matter was filtered off and concentrated under reduced pressure to obtain the desired product as a colorless liquid.
I got g. (2) 2-[p-(pentafluorophenyloxycarbonyl)benzamide]-4-chloro-5-
Synthesis of nitrophenol intermediate: Add 12.4 g of 2-amino-4-chloro-5-nitrophenol, 25 g of p-(pentafluorophenyloxycarbonyl)benzoic acid chloride, and 7.5 g of pyridine to 100 ml of acetonitrile, and stir and reflux. Do it for 4 hours. After filtering out insoluble matter, it is cooled and the resulting precipitate is collected by filtration. This is washed with acetonitrile and dried to obtain 23.4 g of pale yellow target product. (3) 2-[p-(pentafluorophenyloxycarbonyl)benzamide]-4-chloro-5-
Synthesis of aminophenol hydrochloride intermediate, 2-[p-(pentafluorophenyloxycarbonyl)benzamide]- in 200 ml of ethanol.
4-chloro-5-nitrophenol 15.2g and hydrochloric acid
15 ml and 1.5 g of 5% palladium on carbon were added, and catalytic reduction with hydrogen gas was carried out under normal pressure. After absorbing the theoretical amount of hydrogen gas, the catalyst was filtered off and concentrated under reduced pressure to obtain 12.2 g of the desired product as an off-white powder. (4) Synthesis of Exemplified Compound 12 In 100 ml of acetonitrile, 5.0 g of the amine hydrochloride obtained in step (3) and α-(2,4-di-t-
Amylphenoxy)hexanoyl chloride 4.5g
After stirring and refluxing for 5 hours, the reaction solution was concentrated under reduced pressure, added to 300 ml of water, and extracted with 500 ml of ethyl acetate. After washing with water and dehydrating with anhydrous magnesium sulfate, concentrate under reduced pressure. The resulting residue was separated and purified by column chromatography using a mixed solution of toluene and acetone as an eluent to obtain a white target product.
Obtain 2.34g. The structure of the above target product was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry. In order to incorporate the coupler according to the present invention into an emulsion, a conventionally known method may be followed. For example, high-boiling organic solvents with a boiling point of 175°C or higher such as tricresyl phosphate and dibutyl phtate, or butyl acetate,
The coupler of the present invention is dissolved in a low boiling point solvent such as butyl propionate, or in a mixture thereof as necessary, and then mixed with an aqueous gelatin solution containing a surfactant. After emulsifying with a high-speed rotary mixer, ultrasonic disperser or colloid mill, it can be added to silver halide to prepare the silver halide emulsion used in the present invention. When the coupler according to the present invention is added to a silver halide emulsion, the coupler according to the present invention is usually added in an amount of about 0.07 to 0.7 mol, preferably 0.1 mol to 0.4 mol, per 1 mol of silver halide. . The silver halide color photographic material containing the cyan coupler of the present invention may be a monochrome element or a multicolor element. When used in multicolor elements, the cyan dye-forming couplers of this invention are normally included in red-sensitive emulsions, but may also be incorporated into unsensitized emulsions or emulsion layers sensitive to the three primary regions of the spectrum other than red-sensitivity. may be included. Each constituent unit of a multicolor element is
It may consist of either a single emulsion layer or multiple emulsion layers that are 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 comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler (at least one of the cyan dye-forming couplers being a coupler of the invention). ) a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer having at least one magenta dye-forming coupler; at least one blue-sensitive silver halide emulsion having at least one yellow dye-forming coupler; It consists of a yellow pigment image-forming structural unit consisting of layers supported on a support. Silver halide used in the silver halide emulsion of the photosensitive layer in the present invention includes silver bromide,
Any of those used in ordinary silver halide emulsions, such as silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide, are 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, namely, 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 silver bromide or iodobromide. It can be prepared by any manufacturing method such as a so-called compound emulsion manufacturing method such as conversion into a silver salt, or a Lippmann emulsion manufacturing 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 aurithiocyanate, potassium chloroaurate, 2-oresulfobenzthiazole methyl chloride, etc., or sensitization of water-soluble salts such as rutinium, rhodium, iridium, etc. agents, specifically ammonium chloroparadate,
Chemical sensitization can be carried out using 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
Photographic additives such as those described in Research Disclosure December 1978 Item 17643. 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. 2270378, No. 2442710, No. 2442710, No. 2270378, No. 2442710, No.
Typical examples include cyanine dyes, merocyanine dyes, and composite 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-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-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, in combination with black and white developing agents such as hydroquinone and phenidone. 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 regulators such as It may also contain citradinic acid and the like. Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. Example 1 Using couplers of the present invention and comparative couplers as shown in Table 1 below, 0.02 mole for the couplers of the present invention and comparative coupler (A), and 0.02 mol for comparative couplers (B) and (C). Since it is a 4-equivalent coupler, 0.04 mol of each was added to a mixed solvent of 5 ml of dibutyl phthalate and 30 ml of ethyl acetate, and heated at 60°C.
It was heated to completely dissolve. This coupler 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. This coupler dispersion was then added to 500 g of a gelatin monochlorobromide emulsion (containing 20 mole percent silver bromide), coated on a polyethylene-coated paper support and dried to produce the compositions listed in Table 1 below. A total of six types of photosensitive material samples were prepared. Each of the above samples was subjected to wedge exposure according to a conventional method and then processed as follows. Processing steps (30°C) Processing time Color development: 3 minutes and 30 seconds Bleach-fixing: 1 minute and 30 seconds Washing with water: 2 minutes The composition of each treatment is shown below. [Color developer composition 1] 4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 5.0g Benzyl alcohol 15.0ml Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 18.5g 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] Ethylene ditetraacetic acid iron ammonium salt 61.0g Ethylenediaminetetraacetic acid diammonium salt
5.0 g Ammonium thiosulfate 124.5 g Sodium metabisulfite 13.3 g Anhydrous sodium sulfite 2.7 g Water was added 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 results in the table above, Samples 1 to 3 according to the present invention all have excellent color development, good sensitivity and maximum density, and have spectral absorption characteristics similar to that of the comparative coupler (A). It was found that the results were as good as Comparative Sample 4 using . Example 2 Using couplers of the present invention and comparative couplers as shown in Table 2 below, exposure and development were carried out in the same manner as in Example 1 to obtain cyan dye images. For each sample with this dye image, the lightfastness of the image,
Heat resistance and moisture resistance tests were conducted. The above light fastness test was carried out after exposing the resulting dye image to a xenon fademeter for 200 hours, and for heat resistance, after storage at 77°C for 2 weeks, and for humidity resistance, at 60°C and relative humidity. After two weeks of storage at 80%, each was measured, and the residual rate at an initial concentration of 1.0 is expressed as a percentage. Regarding the stain, the rate of increase in blue density in the unexposed area of the sample subjected to the light resistance test was expressed as a percentage. The results obtained are listed in Table 2 below.

【table】

[Table] As is clear from the table above, the comparative coupler (A), which had good color development properties, was significantly inferior, especially in the heat resistance and moisture resistance of dye images, and the comparative coupler (B ) and (D) have problems with light resistance. Furthermore, the comparative coupler (E) is particularly prone to staining, and there is room for improvement in all comparative couplers. In contrast, all the samples according to the present invention using the cyan couplers of the present invention exhibited excellent performance in terms of the above characteristics, and it was understood that the couplers had excellent image storage properties.

Claims (1)

[Claims] 1 A phenolic cyan coupler for photography, which has a benzoylamino group having a fluorinated alkyloxycarbonyl group or a fluorinated phenyloxycarbonyl group at the 2-position of the phenol, and an acylamino group at the 5-position. A characteristic phenolic cyan coupler for photography.