JPH0247735B2 - HAROGENKAGINSHASHINKANKOZAIRYONOSHORIHOHO - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for processing a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a novel cyan dye image-forming coupler. Normally, color images are produced by reducing silver halide grains exposed to light by an aromatic primary amine color developing agent, and couplers that form yellow, magenta, and cyan dyes with the oxidation products of the color developing agent. is formed by oxidative coupling in a silver halide emulsion. Couplers typically used to form cyan dyes are phenols and naphthols. Particularly in the case of phenols, considering the photographic performance of conventional couplers, the basic properties required are that the dye has good spectral absorption characteristics, that is, there is no absorption in the green region of the spectrum and it is sharp. The pigment formed has sufficient fastness against light, heat, moisture, etc. It goes without saying that it has good color development, that is, sufficient color development sensitivity and color development density, but on the other hand, conventionally, a series of steps to obtain an image by imagewise exposure of a silver halide photographic light-sensitive material and development processing is required. It has been a long-held aspiration to speed up the process. As one means for solving this demand, a technique is known in which a bleach-fixing process is performed in which a bleaching process and a fixing process are performed simultaneously. On the other hand, in recent years, aminopolycarboxylic acid metal complex salts (e.g.
A common method is to use EDTA (ferric salt) in the bleach-fixing process, but if you get tired from running,
There is a problem in that the dyes forming the image are likely to be lost (especially cyan dyes). Therefore, there is a strong demand that, for example, bleach-fix baths containing EDTA ferric salt as a main component do not lose color even when fatigued by running. Furthermore, from the viewpoint of depollution, the removal of benzyl alcohol added to color developing solutions has been taken up as a major problem. However, the current situation is that sufficient color development cannot generally be obtained unless benzyl alcohol is added. The decrease in color development due to the removal of benzyl alcohol is particularly noticeable in phenolic cyan couplers, and from this point of view as well, there is a demand for phenolic cyan couplers that exhibit high color development even without benzyl alcohol. Research has been carried out to satisfy the above requirements, but to the best of the knowledge of the present inventors, a cyan coupler that satisfies all of the above required properties has not yet been found. For example, 6-[α-(2,4-di-t-amylphenoxy)butanamide]-2,4-di-chloro-3- described in U.S. Pat. No. 2,801,171
Although methylphenol has good light resistance, it has drawbacks in heat resistance and also suffers from large dye loss in tired bleach-fix solutions. Furthermore, color development is highly dependent on benzyl alcohol, and it is difficult to remove benzyl alcohol from the color developing solution. US Patent No.
2-Heptafluorobutanamide-5-[α-(2,4-di-t-amylphenoxy)hexanamide]phenol described in No. 2895826 has excellent heat resistance and dye loss in a tired bleach-fix bath. However, it is inferior in terms of light resistance and color development. Furthermore, the coupler described in JP-A-53-109630 also has problems in terms of removal of benzyl alcohol and light resistance. Additionally, U.S. Patent No.
No. 3839044, Japanese Patent Application Publication No. 1983-37425, Publication No. 37425, Publication No. 1973-
Publication No. 36894, Japanese Unexamined Patent Publication No. 50-10135, Japanese Patent Publication No. 50-117422
No. 50-130441, No. 50-108841, No. 50-
The phenolic cyan couplers described in Publication No. 120334 and the like are also unsatisfactory in terms of heat resistance and removal of benzyl alcohol. Phenol couplers having a ureido group at the 2-position are described in British Patent No. 1011940 and US Patent No. 3446622, US Patent No. 3996253, and US Patent No.
As described in No. 3758308 and No. 3880661, etc., the cyan dyes formed by these couplers have broad spectral absorption, and furthermore, the absorption maximum is in the relatively short wave region of the red region, so the green color of the spectrum is described. It has considerable absorption in the area, which is not favorable for color reproduction. Although the phenol coupler having a ureido group at the 2-position described in JP-A-56-65134 has considerably improved green absorption in the spectral region,
Other characteristics are still insufficient. Therefore, an object of the present invention is to provide a method for processing silver halide photographic materials, which speeds up the processing of silver halide photographic materials, and which prevents loss of cyan dye even when the processing solution suffers running fatigue. Our goal is to provide the following. As a result of extensive research into these conventional techniques, the present inventors have found that two
A phenylureido group having at least one cyano group in the ortho or meta position, a group that can be eliminated during a coupling reaction with a hydrogen atom or an oxidation product of a color developing agent in the 4th position, and an acylamino group in the 5th position. A silver halide photographic material having a silver halide emulsion layer containing a phenolic cyan coupler is processed through the following steps: (i) imagewise exposure, (ii) color development, and (iii) bleach-fixing. By employing a method for processing silver halide photographic materials containing the following, the objective could be achieved. The cyan coupler in the present invention is more preferably represented by the following general formula []. [In the formula, X is an oxygen atom or a sulfur atom, R ₂
represents a linear or branched alkylene group having 1 to 20 carbon atoms, -CN is at the O-position or m-position relative to the ureido group, and R ₃ represents a halogen atom (particularly preferably chloro, bromine, etc.) or Monovalent organic groups, such as alkyl groups {preferably linear or branched alkyl groups having 1 to 4 carbon atoms (particularly preferably methyl and tert-butyl)}, aryl groups {preferably substituted or unsubstituted phenyl group}, heterocyclic group {preferably a nitrogen-containing heterocycle (particularly preferably,
pyrrolidine, piperidine)}, hydroxy group, alkoxy group {preferably a substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms (particularly preferably methoxy, tert-butyloxy, methoxycarbonylmethoxy group)}, aryloxy group {preferably teeth,
Substituted or unsubstituted phenoxy group} Acyloxy group {preferably substituted or unsubstituted alkylcarbonyloxy group, arylcarbonyloxy group} Mercapto group, alkylthio group {preferably substituted or unsubstituted alkylthio having 1 to 8 carbon atoms group (particularly preferably a methylthio group)}, a nitro group, an acyl group {preferably a carbon number of 1 to 8
an alkylcarbonyl group (particularly preferably an acetyl group, a bivaloyl group)}, an amino group, an alkylamino group {preferably a straight or branched alkylamino group having 1 to 4 carbon atoms (particularly preferably a methylamino group, ethylamino group, tert-butylamino group)}, dialkylamino group (preferably dimethylamino group, diethylamino group), R ₁ is a halogen atom (preferably chloro, bromine),
Alkyl group {preferably a linear or branched alkyl group having 1 to 20 carbon atoms (preferably methyl,
tert-butyl, tert-pentyl, tert-octyl,
dodecyl, pentadecyl)}, aryl group (preferably phenyl), heterocyclic group (preferably nitrogen-containing heterocyclic group), aralkyl group (preferably benzyl, phenethyl), alkoxy group {preferably linear or Branched alkyloxy group having 1 to 20 carbon atoms (especially preferably methoxy, ethoxy, tert-butyloxy, octyloxy, decyloxy, dodecyloxy)}, aryloxy group (preferably phenoxy), hydroxy group, acyloxy group { Preferably, a substituted or unsubstituted alkylcarbonyloxy group, (particularly preferably,
acetoxy), arylcarbonyloxy group (especially preferably benzoyloxy)}, carboxy group, alkoxycarbonyl group (preferably substituted or unsubstituted linear or branched alkyloxycarbonyl having 1 to 20 carbon atoms), aryloxy carbonyl group (preferably substituted or unsubstituted phenoxycarbonyl), mercapto group, alkylthio group (preferably linear or branched substituted or unsubstituted alkylthio having 1 to 20 carbon atoms),
Arylthio group (preferably substituted or unsubstituted phenylthio), alkylsulfonyl group (preferably linear or branched alkylsulfonyl having 1 to 20 carbon atoms), arylsulfonyl group (preferably substituted or unsubstituted benzenesulfonyl) ), acyl group (preferably straight-chain or branched alkylcarbonyl having 1 to 20 carbon atoms, substituted or unsubstituted benzenecarbonyl), acylamino group (preferably straight-chain or branched alkylcarbonyl having 1 to 20 carbon atoms) amide, substituted or unsubstituted benzenecarboxamide), sulfonamide group (preferably a linear or branched substituted or unsubstituted alkylsulfonamide group having 1 to 20 carbon atoms, substituted or unsubstituted benzenesulfonamide group) ,
Carbamoyl group (preferably linear or branched alkylaminocarbonyl having 1 to 20 carbon atoms, substituted or unsubstituted phenylaminocarbonyl),
Sulfamoyl group (preferably 1 to 20 carbon atoms)
straight-chain or branched alkylaminosulfonyl,
substituted or unsubstituted phenylaminosulfonyl)
Z is a hydrogen atom, a group that can be eliminated during a coupling reaction with an oxidation product of a color developing agent, a halogen atom (for example, each atom of chlorine, bromine, fluorine, etc.); , an aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, a sulfonamide group, a succinimide group, etc. in which an oxygen atom or a nitrogen atom is directly bonded to the coupling position, and more specific examples include , U.S. Patent No. 3471563, Japanese Patent Application Publication No. 1973-37425, Japanese Patent Application Publication No. 1973-36894, Japanese Patent Application Publication No. 1972-
No. 10135, No. 50-117422, No. 50-130441, No. 10135, No. 50-117422, No. 50-130441, No.
No. 51-108841, No. 50-120334, No. 52-18315,
For those described in the respective publications such as No. 53-52423 and No. 53-105226, n represents an integer from 0 to 3, m represents an integer from 0 to 4, and l represents an integer of 0 or 1, respectively. ] The cyan coupler according to the present invention is illustrated below, but is not limited thereto. Typical synthesis routes and examples of the couplers according to the present invention are shown below. Synthesis Example 1 (Synthesis of Exemplary Coupler 7) Synthesis of 2-(O-cyanophenyl)ureido-4-chloro-5-{α-(2,4-di-tert-pentylphenoxy)hexanamide}phenol. Disperse 18.9 g of 2-amino-4-chloro-5-nitrophenol in 200 ml of toluene and add 16 g of O-cyanophenyl isocyanate under stirring at room temperature.
100 ml of toluene solution was added. The resulting reaction mixture was boiled and reduced for 1 hour. Thereafter, the mixture was cooled to room temperature, and the crystals were filtered and washed with hot toluene. It was further washed with cold methanol to obtain 31 g of a reaction product with a mp of 251 to 255°C. 33 g of 2-(O-cyanophenyl)ureido-4-chloro-5-nitrophenol was dispersed in 200 ml of THF and catalytically reduced using a palladium-carbon catalyst. After consuming the theoretical amount of hydrogen, add 0.9 ml of pyridine and add 3.7 g of 2-
A solution of (2,4-di-tert-pentylphenoxy)hexanoyl chloride dissolved in 50 ml of THF was added under stirring at room temperature. After the addition was completed, the reaction was continued for an additional hour, and then filtered to remove the catalyst. The liquid was added to ice water containing 10 ml of concentrated hydrochloric acid, and extracted with ethyl acetate. After washing with water, the ethyl acetate layer was separated, dried over sodium sulfate, and concentrated under reduced pressure to obtain an oil. Furthermore, solidify the oil using a mixed solvent of benzene and hexane,
Obtained the object. 2.6 g of white solid with mp 163-168°C was obtained.

[Table] Synthesis Example 2 (Synthesis of Exemplary Coupler 8) Preparation of 2-(m-cyanophenyl)ureido-4-chloro-5-{α-(2,4-di-tert-pentylphenoxy)tetradecanamide}phenol Synthesis. Disperse 18.9 g of 2-amino-4-chloro-5-nitrophenol in 200 ml of toluene and add 16 g of m-cyanophenyl isocyanate under stirring at room temperature.
100 ml of toluene solution was added. The resulting reaction mixture was boiled and refluxed for 1 hour. Thereafter, the mixture was cooled to room temperature, and the crystals were filtered and washed with hot toluene.
Furthermore, after washing with cold methanol, drying (mp255 ~
33g of reaction product at 259°C was obtained. 3.3g of 2-(m
-cyanophenyl)ureido-4-chlor-5-
Nitrophenol was dispersed in 200 ml of THF and catalytically reduced using a palladium-carbon catalyst. After consuming the theoretical value of hydrogen, add 0.9 ml of pyridine and further
4.8g of 2-(2,4-di-tert-pentylphenoxy)tetradecanoyl chloride in THF50
ml solution was added under stirring at room temperature. After the addition was completed, the reaction was continued for an additional hour and then filtered to remove the catalyst. The solution was added to ice water containing 10 ml of concentrated hydrochloric acid, and extracted with ethyl acetate. After washing with water, the ethyl acetate layer was separated, dried over sodium sulfate, and concentrated under reduced pressure to obtain an oil. The reaction composition was purified using silica gel and column chromatography, and solidified using hexane.
2.7 g of white solid with mp 185-188°C was obtained.

〔process〕

Processing step (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 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 1. The relative sensitivity values in the table are expressed with the maximum sensitivity value when processed with color developer [1] being 100.

[Table] As is clear from Table 1 above, samples containing the cyan coupler according to the present invention subjected to bleach-fixing had good sensitivity in both color development with benzyl alcohol and color development without benzyl alcohol. , it can be seen that the maximum density is obtained and is excellent. Furthermore, 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 exhibits excellent color purity with little absorption on the short wavelength side. . Example (2) Using samples obtained in the same manner as in Example (1) above, the light resistance, heat resistance, and moisture resistance of dye images were investigated. The results obtained are shown in Table 2.

[Bleach-fix solution composition]

Ethylenediaminetetraacetate iron ammonium salt
50g ammonium sulfite (40% solution) 50ml ammonium thiosulfate (70% solution) 140ml aqueous ammonia (28% solution) 20ml ethylenediaminetetraacetic acid 4g hydrosulfite 5g Add water to make 1. The maximum reflection density of the cyan dye of the sample obtained after the development process was measured. The results are shown in Table 3. The dye residual rate in the maximum density area was determined as follows. Dye residual rate = Fatigue bleach-fix solution treatment/new bleach-fix solution treatment x 100

【table】

[Table] It is understood from Table 3 that the samples using the coupler according to the present invention were treated with a fatigue bleach-fixing solution and the fading of the cyan dye was small.

Claims (1)

[Scope of Claims] 1. On the support, a phenylureido group having at least one cyano group in the ortho or meta position at the 2-position, a hydrogen atom at the 4-position, or a decoupling reaction with an oxidation product of a color developing agent is formed. A silver halide photographic light-sensitive material having a silver halide emulsion layer containing a phenolic cyan coupler having a releasable group and an acylamino group at the 5-position is subjected to (i) imagewise exposure (ii) color development treatment. (iii) A method for processing a silver halide photographic material, including each step of bleach-fixing.