JPH0239782B2 - - 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 are not susceptible to color development, heat resistance, humidity storage stability, or fading of the dye due to bleaching or bleach-fixing treatment. It cannot be said that the performance is necessarily satisfactory in terms of these points. Furthermore, from the viewpoint of depollution, the removal of benzyl alcohol added to color developing solutions has been taken up 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-
Although 3-methylphenol has good light fastness of the dye, it lacks heat resistance, and the dye is also subject to significant fading 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.
No. 3446622, No. 3758308, No. 3996253, and No. 3880661, etc., but the cyan dyes formed by these couplers have broad spectral absorption and absorption maximum at a relatively short wavelength 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 for color reproduction. 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. Therefore, as a result of extensive research into the above-mentioned conventional technology, the present inventors image-processed a silver halide color photographic light-sensitive material in the presence of a phenolic cyan coupler, which is a compound represented by the following general formula []. It has been found that the above characteristics can be improved by a method of forming a cyan dye image. In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, an acyl group, or a heterocyclic group, and R ¹ and R ² are bonded to each other to form a 5-membered Alternatively, a 6-membered ring may be formed, and R ³ represents a ballast group.
X represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidation product of a color developing agent, and n
is an integer of 0 or 1. The present invention will be explained in more detail below. The phenolic cyan coupler used in the improved cyan dye image forming method of the present invention is as shown in the above general formula [], and the alkyl groups represented by R ¹ and R ² in the general formula [] are Preferably, it is a linear or branched substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, the acyl group is preferably an alkylcarbonyl group or an arylcarbonyl group, and the heterocyclic group is preferably a nitrogen-containing heterocyclic group. It is a ring group. Furthermore, R ¹ and R ² above also represent an aryl group, an alkenyl group, a cycloalkyl group, etc., but these groups represented by R ¹ and R ² may have a substituent, and in this case, the substituent Examples include a halogen atom, a nitro group, a cyano group, an alkyl group, an aryl group, and an alkoxy group. Furthermore, when R ¹ and R ² combine with each other to form a 5- or 6-membered ring, the atoms forming the ring may be selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. can. R ³ represents a ballast group, preferably having 4 carbon atoms
~30 straight-chain or branched alkyl groups (e.g. t-
Butyl group, n-octyl group, t-octyl group, n
-dodecyl group, etc.), alkenyl group, alkoxyalkyl group, cycloalkyl group, 5-membered or 6-membered
It represents a membered heterocyclic group or a group represented by the following general formula [], which may have a substituent. In the formula, J is an oxygen atom or a sulfur atom, R ₃ is a linear or branched alkyl group having 1 to 20 carbon atoms, R ₄
is a hydrogen atom, a halogen atom (preferably chloro, bromo, or , pentadecyl)}, an aryl group (e.g. phenyl), a heterocyclic group (preferably a nitrogen-containing heterocyclic group), an alkoxy group {preferably a linear or branched alkyloxy group having 1 to 20 carbon atoms (e.g. methoxy, ethoxy, tert-butyloxy, octyloxy, decyloxy, dodecyloxy)}, aryloxy groups (e.g. phenoxy),
Hydroxy group, acyloxy group {preferably alkylcarnyloxy group, arylcarbonyloxy group (e.g. acetoxy, benzoyloxy)}, orboxy group, alkoxycarbonyl group (preferably linear or branched alkyl having 1 to 20 carbon atoms) oxycarbol), aryloxycarbonyl group (preferably phenoxycarbonyl), mercapto group, alkylthio group, (preferably linear or branched benzenesulfonyl having 1 to 20 carbon atoms), acyl group (preferably carbon linear or branched alkylcarbonyl having numbers 1 to 20),
Acylamino group (preferably a linear or branched alkylcarboxamide having 1 to 20 carbon atoms, benzenecarboxamide), a sulfonamide group (preferably a linear or branched alkylsulfonamide group having 1 to 20 carbon atoms, benzene) sulfonamide group),
Carbamoyl group (preferably linear or branched alkylaminocarbonyl having 1 to 20 carbon atoms, phenylaminocarbonyl), sulfamoyl group (preferably linear or branched alkylaminosulfonyl having 1 to 20 carbon atoms, phenyl) represents a group arbitrarily selected from each group (aminosulfonyl), and these groups may have a substituent. and Examples include aryloxy groups, carbamoyloxy groups, carbamoylmethoxy groups, acyloxy groups, sulfonamide groups, succinimide groups, and more specific examples include U.S. Pat. No. 37425, Special Publication No. 1972-36894, No. 36894, Special Publication No. 1973
−10135, No. 50-117422, No. 50-130441,
No. 51-108841, No. 50-120334, No. 52-18315
m represents an integer from 1 to 4, and l represents an integer of 0 or 1, respectively. Next, specific examples of the phenolic cyan coupler according to the present invention represented by the above general formula [] will be described, but the present invention is not limited thereto. Synthesis examples of the phenolic cyan coupler according to the present invention will be described below. Synthesis Example 1 2-N-,N-dimethylsulfamide-5-
[Synthesis of α-(2,4-di-t-pentylphenoxy)butanamidophenol (Exemplary Compound 2). 12.4 g of 2-N,N-dimethylsulfamide-5-nitrophenol was added to 300 g of tetrahydrofuran.
ml, and catalytic reduction was performed using a 5% palladium-carbon catalyst. After consuming the theoretical amount of hydrogen,
To this reaction solution was added 7.9 g of pyridine, 2-(2,4-di-
t-Pentylphenoxy)butanoyl chloride
16.9 g was added and stirred at room temperature for 1 hour. After stirring, the above reaction solution was added to ice water and extracted with ethyl acetate. After washing the extract with water, the ethyl acetate layer was separated, dried over sodium sulfate, and concentrated to obtain an extract. The resulting reaction crude product was isolated and purified using silica gel column chromatography. 9.5 g of a colorless solid with a melting point of 130 DEG -131 DEG C. was obtained. Synthesis example 2 2-N-phenylcarbamoylsulfamide-
Synthesis of 5-[α-(2,4-di-t-pentylphenoxy)butanamidophenol (Exemplary Compound 11). 2-N-Phenylcarbamoylsulfamide-
17.6 g of 5-nitrophenol was dissolved in 500 ml of tetrahydrofuran, and catalytic reduction was performed using a 5% 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. Next, it was treated in the same manner as in Synthesis Example 1 above, and the melting point was 137° to 139°.
Obtained 20.3 g of a colorless solid. The structure of the phenolic cyan coupler obtained by the above synthesis method was investigated by IR, NMR and
It was confirmed that it was the target object using various methods of FDMass. Further, other exemplified compounds can also be produced by the same method as above. The cyan dye-forming couplers used in this invention are similarly applicable to the process techniques used for conventional cyan dye-forming couplers. Typically, the coupler is incorporated into a silver halide emulsion and the emulsion is coated onto a base to form the photographic element. Photographic elements can be single color or multicolor elements. In multicolor elements, the cyan dye-forming couplers of this invention are normally incorporated into red-sensitive emulsions;
However, it may be contained in a non-sensitized emulsion or an emulsion layer sensitive to the three primary color regions of the spectrum other than red sensitivity. Each structural unit can consist of 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 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 base supporting a yellow dye image-forming structural unit consisting of layers. The element can have additional layers such as filter layers, interlayers, protective layers, subbing layers, 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 having 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, either alone or in a mixture thereof as necessary. alone or in combination, mixed with an aqueous gelatin solution containing a surfactant, emulsified with a high-speed rotary mixer, ultrasonic disperser or colloid mill, and then added to silver halide to produce the present invention. The silver halide emulsion used can be adjusted. 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 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 conversion 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., or 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 sensitizers of water-soluble salts such as rutinium, rhodium, iridium, etc. Chemical sensitization can be achieved by 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, photographic additives such as those described in Research Diserosure 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, U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in the specifications of No. 2270378, No. 2442710, 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.
The embodiments of the present invention are not limited to this. 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. This solution was added to an aqueous solution of Alkanol B (alkyl group naphthalene sulfonate, manufactured by DuPont) and gelatin, and emulsified using a colloid mill to prepare respective coupler dispersions. Next, this dispersion was added to a silver iodobromide emulsion containing 0.1 mol of silver (6 mol % of silver iodide), coated on a cellulose acetate film base, and dried to form six types of stable coating films. silver halide color photographic light-sensitive materials (sample numbers 1-
6) was 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, trisodium 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. The photographic properties of the cyan dye image obtained by the above processing were measured. The results are shown in Table 1 below.

[Table] (The relative sensitivity in the table is for comparative coupler A.
As is clear from the results in Table 1 above, samples using couplers according to the present invention (sample Nos. 1 to 3)
It can be seen that both sensitivity and color development are superior to the comparative couplers. 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 = fatigued bleach solution treatment/new solution bleach 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.

【table】

〔process〕

Processing steps (30°C), processing time Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Water washing 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 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] Ethylenediaminetetraacetate iron ammonium
50g ammonium sulfite (40% solution) 50g ammonium thiosulfate (70% solution) 140ml ammonium water (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. In addition, as a result of measuring the color spectrum, it was found that the dye using the coupler of the present invention has the maximum absorption in a relatively long part of the red region, and shows excellent color purity with little absorption in the short wavelength side. did it.

Claims (1)

[Scope of Claims] 1. A method of forming a cyan dye image by image processing a silver halide color photographic light-sensitive material in the presence of a phenolic cyan coupler, wherein the cyan coupler is a compound represented by the following general formula []. A cyan dye image forming method characterized by: [In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, an acyl group, or a heterocyclic group, and the above R ¹ and R ² are bonded to each other to form a 5-membered Alternatively, a 6-membered ring may be formed, and R ³ represents a ballast group.
X represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidation product of a color developing agent, and n
is an integer of 0 or 1. ]