JPH0314167B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for forming a cyan dye image, and more particularly to an improved method for forming a cyan dye image capable of forming a cyan dye image with excellent 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. In particular, phenolic cyan couplers are usually considered to have good spectral absorption characteristics and excellent color reproducibility, but they have poor color development, heat resistance,
It cannot be said that they necessarily have satisfactory performance in terms of moisture resistance, storage stability, and fading resistance of dyes accompanying bleaching or bleach-fixing treatments. Furthermore, from the standpoint of depollution, the removal of benzine alcohol added to color developing solutions has been raised as an issue. 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, 6-[α-(2,4-di-t-amylphenoxy)butanamide]-2,4-dichloro-3-
Methylphenol provides a dye with good light resistance, but it lacks heat resistance and the color of the dye is significantly faded in a tired bleach-fix solution. Furthermore, color development is highly dependent on benzyl alcohol, making it difficult to remove benzyl alcohol from the color developing solution. Also, 2-heptafluorobutanamide-5-[α-(2,4-
Di-t-amylphenoxy)hexaneamide]phenol is excellent in terms of heat resistance and fading resistance of dyes in a tired bleach-fixing bath, but has problems with respect to light resistance and color development. Furthermore, phenol couplers having a ureido group at the 2-position are disclosed in British Patent No. 1011940 and US Patent No.
The cyan dyes formed by these couplers have broad spectral absorption, and the absorption maximum is at relatively short wavelengths in the red region. Since it is in the green region of the spectrum, it has considerable absorption in the green region of the spectrum, which is unfavorable in terms of color reproducibility. Although the phenol coupler having a ureido group at the 2-position described in JP-A-56-65134 has been considerably improved in terms of green absorption in the spectral region, it is still unsatisfactory in other properties. As a result of extensive research into the above-mentioned conventional techniques, the present inventors have developed a method for forming a cyan dye image by processing a silver halide color photographic light-sensitive material in the presence of a phenolic cyan coupler. The phenolic cyan coupler has a phenylureido group having at least one substituent represented by the following general formula () or () at the 2-position of the phenol nucleus, and a hydrogen atom or an oxidation product of a color developing agent at the 4-position. It has been found that the above object can be achieved by a cyan dye image forming method characterized by using a cyan coupler substituted with a group capable of leaving during the coupling reaction and an acylamino group at the 5-position. In the formula, R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. The present invention will be explained in more detail below. The phenolic cyan coupler used in the cyan dye image forming method of the present invention has a phenylureido group substituted at the 2-position of its phenol nucleus, and in particular has at least one group represented by the general formula () or () on the nucleus ureido. Replacement, again 4
A cyan coupler having a structure in which a hydrogen atom or a group capable of leaving during the coupling reaction with the oxidation product of a color developing agent is substituted at the position, and an acylamino group is further substituted at the 5th position, and is preferably a cyan coupler having the following general formula ( ) can be shown. In the formula, R ₁ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a hydroxy group, an acyloxy group, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a mercapto group, It represents an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acylamino group, a sulfonamido group, a carbamoyl group, or a sulfamoyl group, R ₂ represents a linear or branched alkylene group, and R ₃ represents a hydrogen atom ,
Represents a halogen atom. Further, X is an oxygen atom or a sulfur atom, Y is a group represented by the above general formula () or (), and Z
represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidation product of a color developing agent. l is 0 or 1, m is 1-4, and n is 0-3
each represents an integer. The alkyl group represented by R in the general formula () or () is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, the aryl group is preferably a phenyl group, and the heterocyclic group is preferably a phenyl group. Preferred is a nitrogen-containing heterocyclic group. In the general formula (), two adjacent R's may be bonded to each other to form a 5- or 6-membered ring. In the general formula (), the halogen atom represented by R ₁ is preferably chlorine or bromine, and the alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, particularly preferably methyl, tert-butyl,
The aryl group is preferably a phenyl group, and the heterocyclic group is preferably a nitrogen-containing heterocyclic group. In addition, the alkoxy group represented by R ₁ is preferably a straight chain or branched carbon number of 1 to 20
an alkyloxy group, particularly preferably methoxy,
Ethoxy, tert-butyloxy, octyloxy, decyloxy, and dodecyloxy groups, the aryloxy group is preferably a phenoxy group, and the acyloxy group is preferably an alkylcarbonyloxy group, an arylcarbonyloxy group, particularly preferably acetoxy, The alkoxycarbonyl group is preferably a linear or branched alkyloxycarbonyl group having 1 to 20 carbon atoms, and the aryloxycarbonyl group is preferably a phenoxycarbonyl group. Furthermore, the alkylthio group represented by R ₁ above is preferably a linear or branched alkylthio group having 1 to 20 carbon atoms, and the acyl group is preferably a linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, The acylamino group preferably has 1 to 1 carbon atoms.
20 linear or branched alkylcarboxamide groups, benzenecarboxamide groups, and the sulfonamide group is preferably a linear or branched alkylsulfonamide group or benzenesulfonamide group having 1 to 20 carbon atoms; The carbamoyl group is preferably a linear or branched alkylaminocarbonyl or phenylaminocarbonyl group having 1 to 20 carbon atoms, and the sulfamoyl group is preferably a linear or branched alkylaminocarbonyl group having 1 to 20 carbon atoms.
~20 linear or branched alkylaminosulfonyl and phenylaminosulfonyl groups, each of which may have a substituent. Next, in the general formula (), the linear or branched alkylene group represented by R ₂ is preferably an alkylene group having 1 to 20 carbon atoms. In addition, in the general formula () above, the group represented by Z that can be dissociated during the coupling reaction is, for example, a halogen atom (specifically, each atom such as chlorine, bromine, fluorine, etc.), an oxygen atom, or a nitrogen atom bonded directly to the coupling position. Examples include aryloxy groups, carbamoyloxy groups, carbamoylmethoxy groups, acyloxy groups, sulfonamide groups, and succinimide groups. Furthermore, specific examples of these groups include, for example, U.S. Pat.
No. 117422, No. 50-130441, No. 51-108841, No. 117422, No. 50-130441, No. 51-108841, No.
No. 50-120334, No. 52-18315, No. 53-52423,
It is described in various publications such as No. 53-105226. Below, the general formula () according to the present invention,
Typical specific examples of phenolic cyan couplers represented by () and () are shown below.
The present invention is not limited to these. Next, typical synthesis steps and synthesis examples of the phenolic cyan coupler according to the present invention will be shown. Synthesis Example 1 Synthesis of 2-(4-diethoxyphosphorylphenyl)ureido-5-{α-(2,4-di-t-pentylphenoxy)hexaneamidophenol (Exemplary Compound 4). 15.4 g of 2-amino-5-nitrophenol,
A mixture of 34.9 g phenyl-4-diethoxyphosphorylphenyl carbamate and 680 mg imidazole, 200 ml toluene was refluxed for 8 hours. After reflux, the precipitated crystals were collected and washed with toluene. 32.7 g of a yellow solid was thus obtained. Obtained 2-(4-diethoxyphosphorylphenyl)
20.5 g of ureido-5-nitrophenol was dissolved in 200 ml of tetrahydrofuran, and catalytic reduction was performed using a palladium-carbon catalyst. After consuming the theoretical amount of hydrogen, add pyridine to the reaction solution.
7.9 g and 18.3 g of 2-(2,4-di-t-pentylphenoxy)hexyl chloride were added, and the mixture was stirred at room temperature for 1 hour. After stirring, the mixture was added to ice water and extracted with ethyl acetate. After washing with water, the ethyl acetate layer was separated, dried over sodium sulfate, and concentrated.
An extract was obtained. This reaction crude product was isolated and purified using a silica gel column cloth to obtain 19.3 g of light brown caramel. Synthesis example 2 2-(4-butylsulfenyl)ureido-5
-{α-(2,4-di-t-pentylphenoxy)butanamidophenol (Exemplary Compound 7)
synthesis of. 15.4 g of 2-amino-5-nitrophenol,
31.7 g phenyl-4-butylsulfinyl phenyl carbamate, 680 mg imidazole and
A mixture of 200 ml of toluene was reacted and treated in the same manner as in Synthesis Example 1, yielding 29.1 g of a yellow solid with a melting point of 144° to 145°C.
I got it. Obtained 2-(4-butylsulfinylphenyl)ureido-5-nitrophenol 18.9
Catalytic reduction of g was carried out in tetrahydrofuran using a palladium-carbon catalyst. After consuming the theoretical amount of hydrogen, 7.9 g of pyridine, 2-(2,4
16.9 g of -di-t-pentylphenoxy)butanoyl chloride was added, and the mixture was stirred at room temperature for 1 hour. After stirring, the same treatment as in Synthesis Example 1 was carried out. 20g melting point
A colorless solid was obtained at 204°-206°C. The structures of the intermediate and cyan coupler synthesized above were confirmed to match the target product by IR, NMR, etc. Other cyan couplers of the present invention can be synthesized in a similar manner. The cyan dye-forming couplers used in the present invention are similarly applicable to the method techniques used for conventional cyan dye-forming couplers. Typically, couplers are incorporated into a silver halide emulsion and the emulsion is coated onto a paste to form a photographic element. Photographic elements can be single color or multicolor elements. In multicolor elements, the cyan dye-forming couplers of this invention are normally included in red-sensitive emulsions, but may also be included in unsensitized emulsions or emulsion layers sensitive to the three primary regions of the spectrum other than red-sensitivity. Good too. Each structural unit can consist of 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 has at least one cyan dye-forming coupler.
a cyan dye image-forming unit consisting of two red-sensitive silver halide emulsion layers (at least one of the cyan dye-forming couplers being a coupler of the invention; at least one green-sensitive silver halide emulsion layer having at least one magenta dye-forming coupler); The element comprises a base-supported magenta dye image-forming unit consisting of an emulsion layer and a yellow dye image-forming unit consisting of at least one blue-sensitive silver halide emulsion layer having at least one yellow dye-forming coupler. , an additional layer e.g. a filter layer,
It can have an intermediate layer, a protective layer, an undercoat layer, etc. In order to incorporate the coupler according to the present invention into an emulsion, a conventionally known method may be followed. For example, the coupler of the present invention may be added to a high boiling point organic solvent with a boiling point of 175°C or higher such as tricresyl phosphate or dibutyl phthalate, or a low boiling point solvent such as butyl acetate or butyl propionate, or a mixture thereof as necessary. After dissolving either alone or in combination, mixing with an aqueous gelatin solution containing a surfactant,
Next, 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 average amount of 0.07 to 0.7 mol, preferably 0.1 mol to 0.4 mol, per 1 mol of silver halide. The silver halide used in the silver halide emulsion in the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc., which are commonly used in silver halide emulsions. Anything is included. The silver halide emulsion constituting the silver halide emulsion used in the present invention can be manufactured by various manufacturing methods including the usual manufacturing method, such as the method described in Japanese Patent Publication No. 46-7772, i.e., the solubility is lower than that of bromide. A method for producing a so-called compound emulsion, such as forming an emulsion of silver salt grains that are larger than silver and consisting of at least a portion of silver salt, and then converting at least a portion of the grains into silver bromide or silver iodobromide salt. ,or
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 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. 2,269,233
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. Development is followed by the usual steps of bleaching, fixing or bleach-fixing, washing and drying to remove silver and silver halides. The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 0.01 mole of each of the phenolic cyan couplers according to the present invention as shown in Table 1 below and the following comparative couplers (A), (B) and (C) were taken,
It was added to a mixture of dibutyl phthalate in an amount equal to its weight and ethyl acetate in an amount three times its weight, and heated to 60°C to completely dissolve it. Add this solution to Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont)
and an aqueous solution of gelatin and emulsified using a colloid mill to create respective coupler dispersions. Next, this dispersion was added to a silver iodobromide emulsion containing 0.1 mol of silver (6 mol % of silver iodide) and coated on a cellulose acetate film base.
Six types of silver halide color photographic materials (sample numbers 1 to 6) having dry and stable coating films were obtained. These samples were subjected to wedge exposure according to a conventional method, and then subjected to the following processing. Processing process (33℃) Processing time Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds [Color developer composition] 4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.8g Anhydrous sodium sulfite 0.14g Hydroxyamine, 1/8 sulfate 1.98g Sulfuric acid 0.74mg Anhydrous potassium carbonate 28.85g Anhydrous potassium bicarbonate 3.46g Anhydrous potassium sulfite 5.10g Potassium bromide 1.16g Sodium chloride 0.14g Nitriloacetic acid, 3 Sodium salt 1.20g Potassium hydroxide 1.48g Add water to make 1. [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
100g Ethylenediaminetetraacetic acid diammonium salt
10g ammonium bromide 150g glacial acetic acid 10ml Add water to make 1, then use ammonia water to pH
Adjust to 6.0. [Fixer composition] Ammonia thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 1, and adjust to PH6.0 using acetic acid. [Stabilizing liquid composition] Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. Photographic characteristics were measured for the cyan dye image obtained by the above processing. The results are shown in Table 1 below.

[Table] As is clear from the results in Table 1 above, samples using couplers according to the present invention (Samples Nos. 1 to 3)
It can be seen that this coupler is superior to the comparative couplers in both sensitivity and color development. Furthermore, as a result of measuring the spectroscopic spectrum, it was found that the sample according to the present invention has a maximum absorption wavelength in the long wavelength region of the red region, exhibits a sharp cut in the short wavelength region, and provides a dye image that is preferable in terms of color reproduction. . Example 2 Samples 1 to 6 obtained in Example 1 were subjected to wedge exposure and then subjected to the color development process of Example 1. On the other hand, development was carried out using a bleach-fix solution with the composition shown below, and the fading resistance of the cyan dye image due to the fatigued bleach solution was investigated. (Bleach solution composition) Ethylenediaminetetraacetic acid iron ammonium salt
100g Ethylenediaminetetraacetic acid diammonium salt
10g ammonium bromide 150g glacial acetic acid 10ml hydrosulfite 5g Add water to make 1, then use 10N sulfuric acid to pH
Adjust to 5.5. The maximum reflection density of the cyan dye of the sample obtained by image processing was measured. The results are shown in Table 2 below. Incidentally, the dye residual rate at the maximum density portion was determined as follows. Dye residual rate = Fatigue whitening solution treatment / New whitening solution treatment x 100

[Table] From the results in Table 2 above, it was understood that the samples using the couplers according to the present invention (Samples Nos. 7 to 9) showed less fading of the cyan dye during fatigue bleaching solution treatment. Example 3 Using a sample obtained in the same manner as in Example 1, the light resistance, heat resistance, and moisture resistance of the dye image were examined. The results obtained are shown in Table 3.

[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 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. [Color developer composition 2] 4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 5.0g 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 use sodium hydroxide. and adjust the pH to 10.30. [Bleach-fix solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
50g ammonium sulfite (40% solution) 50ml ammonium thiosulfate (70% solution) 140ml aqueous ammonia (28% solution) 20ml ethylenediaminetetraacetic acid 4g Add water to make 1. Photographic properties were measured for each of the obtained samples. The results are shown in Table 4 below. In the table, the relative sensitivity values are expressed with the maximum sensitivity value when processed with color developer [1] as 100.

[Table] As is clear from Table 4, the samples obtained using the coupler according to the present invention are excellent in that good sensitivity and maximum density can be obtained regardless of the presence or absence of benzyl alcohol. Furthermore, as a result of measuring the color spectrum, it can be seen that the dye using the coupler of the present invention has a maximum absorption maximum in a relatively long part of the red region, and shows excellent color purity with little absorption on the short wavelength side. Ta.

Claims (1)

[Scope of Claims] 1. A method for forming a cyan dye image by processing a silver halide color photographic light-sensitive material in the presence of a phenolic cyan coupler, wherein the phenolic cyan coupler has a phenol nucleus at the second position,
A phenylureido group having at least one substituent represented by the following general formula () or (),
a hydrogen atom at the 4-position or a group that can be separated during the coupling reaction with the oxidation product of the color developing agent, and a group at the 5-position.
A cyan dye image forming method characterized in that the cyan coupler is substituted with an acylamino group at each position. (In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.) 2. Claim 1, wherein the phenolic cyan coupler is represented by the following general formula (). A cyan dye image forming method as described. (In the formula, R ₁ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a hydroxy group, an acyloxy group, a carboxy group, an alkoxycarbonyl group, an aryl group, an oxycarbonyl group, mercapto group,
It represents an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acylamino group, a sulfonamido group, a carbamoyl group, or a sulfamoyl group, R ₂ represents a linear or branched alkylene group, and R ₃ represents a hydrogen atom Or represents a halogen atom. In addition, X is an oxygen atom or a sulfur atom, Y is a group represented by the following general formula () or (), In the formula, R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Z represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidation product of a color developing agent. l is 0 or 1, m is 1-4, and n is 0-3
each represents an integer. )