JPH0135337B2 - - 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. . 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 phenol 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 to form an emulsion. added inside. 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 viewpoint 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 present inventor's knowledge, among the 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-
As is clear from the examples below, 3-methylphenol has good light resistance, but has a drawback 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 developing solution is insufficient. Moreover, 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 the terminal of the substituent at the 5 position is p-alkylsulfonylamino group. 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 The color dependence on alcohol is large,
Improvements in this respect are desired. 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, also have problems with heat resistance, or the rate of dye formation in color developing solutions that exclude benzyl alcohol. Also, the maximum coloring density is insufficient, so that it does not satisfy all the properties required of a cyan coupler. Accordingly, 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 objects of the present invention and other objects described below are achieved by making a cyan coupler represented by the following general formula [] exist when image-processing a silver halide color photographic material to obtain a cyan dye image. . General formula [] (In the formula, R represents a lower alkylene group, R ₁ represents an arylthio group, an arylsulfinyl group, an acylamino group having a thio group, an acylamino group having a sulfinyl group, or a halogen atom, and R ₂ represents an alkyl group or an aryl group. , R ₃ represents a hydrogen atom or a halogen atom, X represents an arylene group, Z represents a hydrogen atom or a coupling-off group, and n represents an integer of 1 or 2.) More details about the cyan coupler represented by the general formula [] Explain. The lower alkylene group represented by R has 1 carbon atom including the branched part.
~20 are preferred, and may be linear or branched, such as methylene, ethylene, 1-
Examples include groups such as methylethylidene, butylene, isobutylene, and tridecylidene. Examples of the group represented by R ₁ include phenylthio and phenylsulfinyl groups. Further, examples of the group substituted with R ₁ in the general formula [] include a group selected from aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues; Hydrogen residues can be either saturated or unsaturated,
Further, it may be linear, branched, or cyclic. Preferred are alkyl groups (eg, methyl, ethyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.) and alkenyl groups (eg, 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, arylazo, Examples include groups such as acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino. ] More specific examples of R ₂ include alkyl groups such as methyl, ethyl, isopropyl, butyl, ter-butyl, dodecyl, pentadecyl, and cyclohexyl, and aryl groups such as phenyl and naphthalene. It is. Further, examples of substituents for each of these groups include halogen atoms (chlorine, bromine, fluorine, etc.), 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. Examples of the above-mentioned arylene group of X include phenylene, methylene, and the like. Furthermore, the following substituents may be substituted. For example, alkoxy groups (e.g. methyl, ethyl, isobutyl, dodecyl, ter-acyl, 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. 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
Those described in various publications such as No. 1, No. 53-52423, and No. 53-105226 are useful. 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 low color dependence on benzyl alcohol from the viewpoint of depollution, that is, color development processing that excludes benzyl alcohol is possible. It has properties such as a fast dye formation rate in liquid and a high color density. However, U.S. Pat.
Moreover, the coupler of the present invention is not even suggested in U.S. Patent No. 3998642, U.S. Patent No. 3839044, or Japanese Patent Application Laid-open No. 109630/1983, etc.
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 in that, among other things, the dependence of color development on benzyl alcohol in the color development processing solution is improved, and furthermore, the image storage stability is improved. Next, typical examples of the coupler of the present invention will be given, but the coupler of the present invention used in the present invention is not limited to these.

【table】

【table】

【table】

[Color developer composition]

[4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 5.0 g Sodium sulfite (anhydrous) 2.0 g Sodium carbonate (monohydrate) 50 g Potassium bromide 1.0 g Potassium hydroxide 0.55 g 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 Water washing...3 minutes 15 seconds Fixation...6 minutes 30 seconds Water 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 as follows, for example. [Color developer composition] [4-Amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.8g Anhydrous sodium sulfite 0.14g Hydroxyamine, 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, 3 Sodium salt (monohydrate)
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] [Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to 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. ] Next, a typical example of a color development process in which the present invention can be used for processing internal color positive light-sensitive materials will be shown. [Processing process] [Processing process (30℃) Processing time Color development...3 minutes 30 seconds Bleach fixing...1 minute 30 seconds Water washing...2 minutes Stabilization...1 minute] The composition of each processing solution that can be used in the above processing steps is , for example 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 Adjust the pH to 10.30 using sodium oxide. ] The above color developer (1) has a color developer composition excluding benzyl alcohol, and the color developer (2) has a conventional color developer composition to which benzyl alcohol is added. 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 use sodium acetate
Adjust to PH3.5~4.0. ] Furthermore, the image forming method of the present invention is disclosed in Japanese Patent Publication No. 1973-
Publication No. 46419, Patent Application No. 70907 (Sho 49-70907)
7929), No. 49-80321 (Unexamined Japanese Patent Publication No. 51-16023), No. 49
It can also be advantageously applied to photosensitive materials used in so-called image reinforcement processing methods described in various publications such as No. 109213 (Japanese Patent Laid-Open 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 mole percent silver bromide) emulsion, coated on polyethylene-coated paper and dried to form a stable coating of six halogens. Silver halide color photographic light-sensitive materials (sample numbers [1] to [7]) were obtained.The six types of silver halide color photographic light-sensitive materials obtained were subjected to wedge exposure according to a conventional method. As a specific example, color development was carried out according to the color development treatment process for internal color positive described above to obtain a cyan color image.The color developer was one to which benzyl alcohol was added [the color developer (2) above]. ] and one without additives [color developing solution (1)].The photographic properties of each of the obtained samples were measured.The results are shown in Table 1.

[Table] In the table, the sensitivity is shown as a relative value when the sensitivity in the benzyl alcohol addition system of sample (4) 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 (as described in West German Publication No. 3017497) Comparative coupler [D ] 2-benzamide-5-[α-[3-(N-butanesulfonyl-N-benzylamino)phenoxy]tetradecanamide}phenol (West German Publication
3017500) As is clear from Table 1 above, the samples processed by the image forming method of the present invention have favorable spectral absorption characteristics, and can be obtained in a color developer system without benzyl alcohol. It can be seen that the maximum density of the color image obtained is greater than that of any of the comparative couplers [A], [B], [C], and [D]. Example (2) Samples 8 to 14 of six kinds of photosensitive materials for forming cyan colored images were obtained in the same manner as in Example (1) above, 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 exposing each obtained image to a xenon fademeter for 200 hours, with the density before exposure being 100. Moisture 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. For comparison couplers [B], [C], and [D], comparison coupler [A]
Although this coupler has improved heat resistance, it still has problems with light resistance in systems without benzyl alcohol. On the other hand, exemplary couplers [3], [7],
[8] is the above comparative coupler [B], [C], [D]
It has heat resistance equivalent to that of 100%, and an improvement in light resistance is observed. Example (3) 10 g of the exemplary coupler [5] or the comparative coupler [A] of the present invention was added to a mixture of 25 ml of dibutyl phthalate and 20 ml of ethyl acetate, and the mixture was heated to 60°C to completely dissolve the mixture. Dissolved. This solution was mixed with 5 ml of a 10% aqueous solution of Alkanol B and 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),
Samples 15 and 16 of silver halide photographic materials having stable coating films were obtained by coating on a cellulose acetate film base and drying. 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.

[Table] As is clear from Table 3, the sample using the coupler of the present invention has a large maximum density.
Moreover, the sample according to the present invention had a cyan negative color image with excellent transparency. Example (4) The above exemplary coupler which is a coupler of the present invention

[9] was incorporated into a conventional high-sensitivity silver iodobromide emulsion for negative use by the Fisher dispersion method (0.2 mole amount was used per 1 mole of silver halide), and this emulsion was coated and dried on a triacetate film base by a conventional method. . The sample thus obtained was exposed in the same manner as in Example (1), and then processed for 3 minutes at 24°C using an alkaline developer having the following composition. [Developer composition] Sodium sulfite 20g 4-N-ethyl-N-β-hydroxyethylaminoaniline 11.0g Adjust to 1 with water. In this development, the image-receiving layer of the image-receiving material, which has an image-receiving layer containing dimethyl-β-hydroxyethyl-γ-stearamidopropylammonium-hydrodiene phosphate on polyethylene-coated paper, and the photosensitive layer of the above sample. were kept in close contact with each other, and the image-receiving material was peeled off after development. As a result, a cyan positive image with a large maximum density, clear image, and excellent photographic properties was obtained on the image-receiving material as in Examples (1), (2), and (3) above, and the coupler of the present invention was used as a coupler for the diffusion transfer method. It was confirmed that it also has excellent properties. Example (5) Exemplary coupler (10) was dissolved in methanol, and this was added to prepare an external color developer having the following composition. External color developer N,N-diethyl-2-methyl-p-phenylenediamine 2.0g Anhydrous sodium sulfite 2.0g Sodium carbonate (monohydrate) 20.0g Potassium bromide 1.0g Exemplary coupler (10) 2.0g Water So let's set it to 1. A sample obtained by coating a high-sensitivity silver iodobromide emulsion on a subbed polyethylene terephthalate film was exposed to light in a conventional manner and then developed for 30 minutes at 24° C. with the above-mentioned external color developing solution. After development, each treatment was carried out in the usual manner: washing with water for 4 minutes, bleaching for 5 minutes, washing with water for 5 minutes, fixing for 5 minutes, washing with water for 30 minutes, and drying, and the maximum absorption was 650 nm.
A cyan image with excellent spectral absorption characteristics and other photographic characteristics was obtained.

Claims (1)

[Scope of Claims] 1. A method for forming a cyan dye image, which comprises image-processing a silver halide color photographic light-sensitive material in the presence of a cyan coupler represented by the following general formula []. General formula [] (In the formula, R represents a lower alkylene group, R ₁ represents an arylthio group, an arylsulfinyl group, an acylamino group having a thio group, an acylamino group having a sulfinyl group, or a halogen atom, and R ₂ represents an alkyl group or an aryl group. , _R3 represents a hydrogen atom or a halogen atom, X represents an arylene group, Z represents a hydrogen atom or a coupling-off group, and n represents an integer of 1 or 2.)