JPH0135338B2 - - 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 a method for forming a cyan dye image by developing a color photographic material in the presence of a novel 2,5-diacylamino cyan coupler. be. More specifically, it has good solubility, dispersion stability, and spectral absorption characteristics, and in particular, has a high dye formation rate in a color development processing solution that excludes benzyl alcohol, has a high color density, and has excellent image storage stability. The present invention relates to a method of forming cyan dye images in the presence of novel cyan couplers. As is well known, subtractive color photography uses aromatic
A grade amine color developer oxidatively couples the oxidation products of the color developer produced by reducing exposed silver halide grains with couplers that form yellow, cyan, and magenta dyes in a silver halide emulsion. A color image is thereby formed. In these cases, as a yellow coupler for forming a yellow dye, a compound having an open-chain active methylene group is generally used, and as a magenta coupler for forming a magenta dye, a pyrazolone type,
Compounds such as pyrazolinobenzimidazole and indazolone are used, and compounds having phenolic and naphtholic hydroxyl groups are used as cyan couplers to form cyan dyes. Each coupler is dissolved in a substantially water-insoluble high-boiling organic solvent or in combination with an auxiliary solvent if necessary, and added to the silver halide emulsion, or dissolved in an aqueous alkaline solution. Added to emulsion. The former is an oil droplet dispersion method, and the latter is an alkali dispersion method, but the former is generally considered to be superior to the latter in terms of light resistance, heat resistance, moisture resistance, granularity, color sharpness, etc. The basic properties required for each coupler are:
In addition to simply forming dyes, the dyes must first have high solubility in high-boiling organic solvents or alkalis, and have good dispersibility and stability in silver halide photographic emulsions. , fastness against heat, moisture, etc., good spectral absorption characteristics, good transparency, high color density, and clear images. It is desired to have the following characteristics. In particular, cyan couplers require improvements in image storage properties such as heat resistance, moisture resistance, and light resistance. Furthermore, from the standpoint of depollution in recent years, the removal of benzyl alcohol added to color development processing solutions has been raised as a major problem. However, in general, when a color developing solution to which benzyl alcohol is not added is used, the present situation is that the color development properties of the coupler added to the silver halide photographic emulsion, that is, the rate of dye formation and the maximum color development density are reduced.
This tendency is particularly evident in cyan couplers. Therefore, it is strongly desired that the color development of this cyan coupler does not depend on benzyl alcohol, and research has been carried out to improve this as well as to improve the above-mentioned image storage stability. However, to the best of the inventor's knowledge,
Among conventionally known cyan couplers, a coupler that satisfies all of the above-mentioned required properties has not yet been found. That is, conventionally known cyan couplers include the following. For example, U.S. Patent No.
The following coupler described in No. 2801171 6-[α-(2,4-di-tert-amylphenoxy)butanamide]-2,4-di-chloro-3
-As is clear from the examples below, methylphenol has good light resistance, but it has shortcomings in heat resistance.In addition, it is highly dependent on benzyl alcohol for color development, and color development that excludes benzyl alcohol is difficult. The maximum color density in the processing solution is insufficient. Furthermore, the coupler described in JP-A-53-109630 is a coupler in which dicarbonylamino groups are substituted at the 2 and 5 positions of phenol, and p-alkylsulfonylamino groups are substituted at the end of the 5-position substituent. It has been described that the stability of dispersion during coating or at the end of coating was improved by introducing an enoxy group or p-alkylaminosulfonylphenoxy group, but as is clear from the examples below, benzyl alcohol still The greater the dependence of color development on the color, the more desirable is the improvement in this respect. Furthermore, U.S. Patent No. 3839044, JP-A-47-
Publication No. 37425, Japanese Patent Publication No. 1983-36894, Japanese Patent Publication No. 1973
−10135, No. 50-117422, No. 50-130441,
Phenol-type cyan couplers, such as those described in Publications No. 50-108841 and No. 50-120334, may also have problems with heat resistance, or may have problems with dye formation speed in color developing solutions that exclude benzyl alcohol. The maximum coloring density may be insufficient, and thus it does not satisfy all the properties required of a cyan coupler. Therefore, a first object of the present invention is to provide a cyan coupler having desirable characteristics required for a cyan coupler as described above. A second object of the present invention is to provide a cyan coupler that has excellent solubility in alkali or high-boiling organic solvents, dispersibility in silver halide color photographic emulsions, and stability. The third object of the present invention is to provide a cyan dye that has excellent image storage properties, that is, heat resistance, light resistance, and moisture resistance, and also has a high dye formation rate in a color development processing solution that excludes benzyl alcohol, and has a high color density. It is an object of the present invention to provide a method for forming a cyan dye image that provides an image. The above object of the present invention is to provide a method for forming a cyan dye image by image processing a silver halide color photographic light-sensitive material in the presence of a 2,5-diacylaminophenol cyan coupler. This is achieved by the presence of a coupler. General formula [] [In the formula, R is a lower alkylene group, R ₁ is an aryl group, acyl group or carbamoyl group, R ₂
is an alkyl group or an aryl group, _R3 is a hydrogen atom or a halogen atom, X is an arylene group,
Z represents a hydrogen atom or a coupling-off group. ] The aryl group represented by R ₁ in the above general formula [] includes phenyl group, naphthyl group, etc. Substituents introduced into these groups include halogen atom, nitro, hydroxy, carboxyl, amino, substituted Examples include amino, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino. Furthermore, the acyl group and carbamoyl group represented by R ₁ in the general formula [] are

[expression] or

[Formula], R', R'', and R include, for example, a group selected from a hydrogen atom, an aliphatic hydrocarbon residue, an aryl group, or a heterocyclic residue, and an aliphatic Hydrocarbon residues may be either saturated or unsaturated,
Further, it may be linear, branched, or cyclic. Preferred are alkyl groups (for example, methyl, ethyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.) and alkenyl groups (for example, allyl group).
Aryl groups include phenyl and naphthyl groups, and representative heterocyclic residues include pyridinyl, quinolylthienyl, piperidyl, imidazolyl and the like. These aliphatic hydrocarbon residues,
Examples of substituents introduced into aryl groups and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, aryloxy, arylthio, and arylazo. , acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, morpholino and the like. Further, R'' and R may form a ring. More specific examples of _R2 include alkyl groups such as methyl, ethyl, isopropyl, butyl, tert-butyl, dodecyl, pentadecyl, cyclohexyl, etc. Examples of the group, aryl group include phenyl, naphthalene, etc.Furthermore, examples of substituents for each of these groups include halogen atoms (chlorine, bromine, fluorine, etc. atoms), nitro group, hydroxy group, Carboxy group, amino group,
Examples include sulfo group, cyano group, alkoxy group, aryloxy group, arylthio group, acylamino group, carbamoyl group, ester group, acyl group, acyloxy group, sulfonamide group, sulfamoyl group, sulfonyl group, sulfoxy group, oxysulfonyl group, etc. It will be done. Further, the arylene group of the above-mentioned group X represents groups such as phenylene and naphthylene, and these arylene groups may be substituted with the following substituents. For example, alkyl groups (e.g. methyl, ethyl, isobutyl, dodecyl, tert-amyl, cyclohexyl, pentadecyl, etc.), alkenyl groups (e.g. allyl), aryl groups, heterocyclic residues, Halogen atoms (e.g. chlorine, bromine, fluorine, etc.), nitro groups, hydroxy groups, carboxy groups, amino groups, sulfo groups, alkoxy groups, aryloxy groups, arylthio groups, acylamino groups, carbamoyl groups, ester groups, acyl group, acyloxy group, sulfonamide group, sulfamoyl group, sulfonyl group, morpholino group, and the like. In addition, R has 1 to 1 carbon atoms including branched parts.
The 20 lower alkylene groups may be either linear or branched. Z represents a hydrogen atom or a coupling-off group, and specific examples of the coupling-off group include a halogen atom (e.g., chlorine, bromine, fluorine, etc. atoms), an oxygen atom, or a nitrogen atom directly bonded to the active site. Aryloxy group, carbamoyloxy group, carbamoylmethoxy group, acyloxy group, alkyloxy group, sulfonamide group,
Examples include succinimide groups, and more specific examples include U.S. Pat.
Publication No. 37425, Japanese Patent Publication No. 1983-36894, Japanese Patent Publication No. 1973
−10135, No. 50-117422, No. 50-130441,
No. 51-108841, No. 50-120334, No. 52-18315
No. 53-52423, No. 53-105226, etc. are useful. The compound represented by the general formula [] has an acylamino group at the 2-position and the 5-position of the phenol, and further has groups such as R ₁ and X defined in the general formula [] as substituents on the acylamino group. It is considered that various good properties were obtained by introducing the defined group. That is, the coupler of the present invention has good solubility in alkali or high-boiling organic solvents, has good dispersion stability in photographic emulsions, has good spectral absorption characteristics, has good transparency, and further contains the coupler of the present invention. The color emulsion according to the present invention has good image storage stability, that is, heat resistance, moisture resistance, and light resistance, and has less dependence of color development on benzyl alcohol from the viewpoint of depollution, that is, it is a color development processing solution that excludes benzyl alcohol. It has properties such as a high rate of pigment formation and high color density. However, U.S. Pat.
Also US Patent No. 3998642, US Patent No. 3839044
No. 53-109630, etc.,
The coupler of the present invention was not even suggested, and as will be clear from the Examples described below, the effect exhibited by the coupler of the present invention was completely surprising. The coupler of the present invention is characterized by improved color development dependence on benzyl alcohol in a color development processing solution, and further improved image storage stability, particularly light resistance. Next, typical examples of the coupler of the present invention will be listed, but the coupler of the present invention used in the present invention is not limited to these.

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【table】

[Color developer composition]

4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 5.0g Sodium sulfite (anhydrous) 2.0g Sodium carbonate (monohydrate) 50g Potassium bromide 1.0g Potassium hydroxide 0.55g Add water to make 1. The coupler of the present invention contained in the color emulsion used in the present invention reacts with the oxidation product of the color developing agent produced when silver halide is developed with such a color developer to form a cyan dye. . After such color development processing, conventional photographic processing is carried out, such as a stop solution containing an organic acid, a stop fix solution containing an organic acid and a fixing component such as hypo or ammonium thiosulfate, a fixing component such as hypo or ammonium thiosulfate, etc. a fixer containing a second aminopolycarboxylic acid;
With processing solutions such as bleaching solutions mainly containing iron salts and alkali halides, bleach-fixing solutions containing fixing components such as ferric salts of aminopolycarboxylic acids and sodium thiosulfate or ammonium thiosulfate, and other stabilizing solutions. Each treatment selected from treatment, washing with water, drying, etc. may be performed in an appropriate combination. Next, a typical example of a color development process in which the present invention can be used to process internal color negative light-sensitive materials will be shown. [Processing process] Processing process (33℃) Processing time Color development…3 minutes 15 seconds Bleaching…6 minutes 30 seconds Washing…3 minutes 15 seconds Fixing…6 minutes 30 seconds Washing…3 minutes 15 seconds Stabilization…1 minute 30 seconds The composition of each treatment liquid that can be used in the treatment step is, for example, as follows. [Color developer composition] 4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.8g Anhydrous sodium sulfite 0.14g Hydroxylamine, 1/2 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 (monohydrate 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 and use ammonia water
Adjust to PH6.0. [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) 1.5 ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5 ml Add water to make 1. Next, a typical example of a color development process in which the present invention can be used to process internal color positive light-sensitive materials will be shown. [Processing process] Processing process (30°C) Processing time Color development...3 minutes 30 seconds Bleach fixing...1 minute 30 seconds Washing...2 minutes Stabilization...1 minute The composition of each processing solution that can be used in the above processing steps is as follows, for example: It is as follows. [Color developer composition (1)] 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. [Color developer composition (2)] 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 using sodium oxide
Adjust to PH10.30. The color developer (1) has a color developer composition excluding benzyl alcohol, and the color developer (2) has a composition that excludes benzyl alcohol.
This is a conventional color developer composition containing conventional benzyl alcohol. When the present invention is used to process internal color positive light-sensitive materials, both of the above color developing solutions (1) and (2) can be used, but from the viewpoint of pollution prevention, the use of the above color developing solution (1) is particularly preferred. In the present invention, good photographic properties can be obtained by using this desirable color developer (1). [Bleach-fix solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
61.0g Ethylenediaminetetraacetic acid diammonium salt
5.0g Ammonium thiosulfate 124.5g Sodium metabisulfite 13.3g Anhydrous sodium sulfite 2.7g Add water to make 1. [Stabilizing liquid composition] Glacial acetic acid 20ml Add water to make 1, and adjust the pH to 3.5-4.0 using sodium acetate. Further, the image forming method of the present invention is
Publication No. 46419, JP-A-51-7929, JP-A No. 51-16023
The present invention can also be advantageously applied to photosensitive materials used in so-called image reinforcement processing methods described in various publications such as No. 51-36136. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereby. Example (1) Using the couplers of the present invention as shown in Table 1 below (indicated by the numbers of the specific examples above) and the following comparative couplers [A], [B], [C], [D], 10 g of each coupler was added to a mixture of 2.5 ml of dibutyl phthalate and 20 ml of ethyl acetate, and the mixture was heated to 60°C to completely dissolve. Add this solution to Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont)
5 ml of 10% aqueous solution of and 200 ml of 5% gelatin aqueous solution
ml and emulsified using a colloid mill to create a dispersion of each coupler. This coupler dispersion was then added to 500 g of gelatin-silver chlorobromide (containing 20 mol% silver bromide) emulsion, coated on polyethylene-coated paper and dried to obtain 10 types with stable coatings. Silver halide color photographic materials (sample numbers [1] to [10]) were obtained. Samples of the 10 types of silver halide color photographic light-sensitive materials obtained were subjected to wedge exposure according to a conventional method, and then, as a specific example, color development was performed according to the color development process for internal color positives described above. A cyan colored image was obtained. Two types of color developing solutions were used: one containing benzyl alcohol (color developing solution (2)) and one without benzyl alcohol (color developing solution (1)). Photographic properties were measured for each of the obtained samples. The results are shown in Table 1.

[Table] Note that the sensitivities in the table are shown as relative values when the sensitivity in the benzyl alcohol addition system of sample 7 using comparative coupler [A] is set as 100. The structures of comparative couplers [A], [B], [C] and [D] are as shown below. Comparative coupler [A] 6-[α-(2,4-di-tert-amylphenoxy)butanamide]-2,4-di-chloro-3
-Methylphenol (described in the above-mentioned U.S. Pat. No. 2,801,171) Comparative coupler [B] 2-benzamide-5-[α-(4-butylsulfonylaminophenoxy)tetradecanamide]phenol (described in the above-mentioned JP-A-53-1999) Comparative coupler [C] 2-benzamide-5-{α-[4-(p-dodecylbenzenesulfonamide)phenoxy]butanamide}phenol (described in West German Publication No. 3017497) Comparative coupler [D] 2-benzamide-5-{α-[3-(N-butanesulfonyl-N-benzylamino)phenoxy]tetradecanamide}phenol (described in West German Publication No. 3017500) Evidently from Table 1 above As shown, the sample processed by the image forming method of the present invention has favorable spectral absorption characteristics, and in a color developer system without benzyl alcohol added, the maximum density of the color image obtained is that of the comparative coupler [A], [B], [C], [D]
It can be seen that it is larger than both. Example (2) Ten types of samples 11 to 20 of photosensitive materials for forming cyan colored images were obtained in the same manner as in Example (1), and their light resistance, heat resistance, and moisture resistance were examined. The results obtained are shown in Table 2.

[Table] In addition, the light resistance in the table is expressed as the residual density after 200 hours of exposure of each image obtained using a xenon fademeter, with the density before exposure being 100. Furthermore, the humidity resistance was expressed as the residual concentration after storage for two weeks at 50° C. and 80% relative humidity, with the concentration before the test being 100.
Furthermore, heat resistance was expressed as the residual concentration after storage for 2 weeks under 77°C, with the concentration before the test being 100. As is clear from Table 2, comparative coupler [A]
Although it has excellent light resistance, it still has problems with heat resistance and moisture resistance. Comparative couplers [B], [C], and [D] are couplers with improved heat resistance compared to comparative coupler [A], but they still have problems with light resistance in systems without benzyl alcohol. ing. On the other hand, exemplary couplers [1], [10],
[12], [15], [22], and [25] have the same heat resistance as the above-mentioned comparative coupler [B], and the effect of improvement in light resistance is recognized. Example (3) 10 g of the exemplary couplers [11], [16] or the comparative coupler [A] which are the couplers of the present invention
was added to a mixture of 2.5 ml of dibutyl phthalate and 20 ml of ethyl acetate, and the mixture was heated to 60°C to completely dissolve. Add this solution to 5 ml of a 10% aqueous solution of Alkanol B.
The mixture was mixed with 200 ml of a 5% aqueous gelatin solution and emulsified using a colloid mill to prepare a coupler dispersion. Next, this dispersion was added to 500 g of negative high-sensitivity gelatin silver iodobromide emulsion (containing 6.0 mol% silver iodide), coated on a cellulose acetate film base, and dried to form a stable coating film. Samples 21, 22, and 23 of silver photographic materials were obtained. This silver halide photographic light-sensitive material was exposed in the same manner as in Example (1), and color development was performed according to the above-described color development process for internal color negatives to obtain a cyan color image. Photographic properties of the obtained cyan colored image were measured. The results are shown in Table 3.

[External color developer]

4-Amino-3-methyl-N,N-diethylaniline 2.0g Anhydrous sodium sulfite 2.0g Sodium carbonate (monohydrate) 20.0g Potassium bromide 1.0g Exemplary coupler 2.0g Set to 1 with water High-sensitivity iodobromide A sample obtained by coating a silver emulsion onto a subbed polyethylene terephthalate film was exposed to light in a conventional manner, and then developed with the external color developing solution at 24° C. for 30 minutes. After development, wash with water for 4 minutes, bleach for 5 minutes, and
When the following treatments were carried out in sequence: washing with water for 5 minutes, fixing for 5 minutes, washing with water for 30 minutes, and drying, a cyan image having excellent spectral absorption characteristics with an absorption maximum of 670 nm and excellent other photographic characteristics was obtained.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material made of 2,5-
A method for forming a cyan dye image by image processing in the presence of a diacylaminophenol cyan coupler, wherein the cyan coupler is represented by the following general formula []. General formula [] [In the formula, R is a lower alkylene group, R ₁ is an aryl group, acyl group or carbamoyl group, R ₂
is an alkyl group or an aryl group, _R3 is a hydrogen atom or a halogen atom, X is an arylene group,
Z represents a hydrogen atom or a coupling-off group. ]