JPS6340303B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for forming a cyan dye image, and in particular 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, minute stability, and spectral absorption characteristics, and in particular, has a high dye formation rate in a color development processing solution that excludes benzyl alcohol, and has a high color density.
Moreover, the present invention relates to a method of forming a cyan dye image in the presence of a novel cyan coupler which has excellent image storage stability. 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 and added to the emulsion. added to. 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. Various properties such as fastness against heat and moisture, good spectral absorption characteristics, good transparency, high color density, and sometimes clear images. It is desired to have the following. 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 development processing solution to which benzyl alcohol is not added is used, the color development properties of the coupler added to the silver halide photographic emulsion, that is, the speed 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 6-[α-(2,4-di-tert-amylphenoxy)butanamide]-2,4-di-chloro-3- described in No. 2801171
As is clear from the examples below, 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 processing that excludes benzyl alcohol is difficult. The maximum color density in the liquid 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 the terminal of the substituent at the 5 position is p-alkylsulfonylamino. It is described that the stability of dispersion during coating or at the end of coating was improved by introducing a phenoxy group or p-alkylaminosulfonylphenoxy group, but as is clear from the examples described later, The greater the dependence of color development on benzyl alcohol, the more desirable is improvement in this respect. In addition, the coupler described in German Patent Publication No. 3017497 has improved color development properties in a color development processing solution that excludes benzyl alcohol of the coupler described in the above-mentioned Japanese Patent Application Laid-Open No. 109630/1982. Although this coupler has been able to reduce the dependence of color development on benzyl alcohol, it is still insufficient and 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. The second object of the present invention is to provide a silver halide material having excellent solubility in alkali or high-boiling organic solvents, dispersibility in silver halide color photographic emulsions, and stability.
The object of the present invention is to provide an equivalent cyan coupler. 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 can be achieved by including a cyan coupler represented by the following general formula [] or [] in the image forming process of a silver halide color photographic light-sensitive material. General formula [] General formula [] [In the formula, R ₁ and R ₁ ' are an alkoxy group or an aryloxy group, B and B' are an alkylene group,
arylene group or divalent heterocyclic group, R ₂ and R ₂ ' are alkylene groups, R ₃ and R ₅ are alkyl groups, aryl groups, or heterocyclic groups, R ₄ and
R ₄ ' is a hydrogen atom or a halogen atom, Z and
Z' represents a group (excluding a hydrogen atom) that can be eliminated during a coupling reaction with an oxidation product of a color developing agent. n represents 0 or 1, and when n is 0, B
represents an arylene group. Further, when B is a phenylene group, R ₁ is bonded to the benzene nucleus at the 2- or 3-position relative to the bonding position of -CONH- or -OR ₂ -. ] The couplers of the present invention represented by the above general formulas [] and [] will be explained in detail below. The alkoxy group represented by R ₁ and R ₁ ' preferably has 1 to 20 carbon atoms, may be substituted, and may be linear or branched. Further, as the aryloxy group, a phenyloxy group is preferable. The alkylene group represented by B and B' preferably has 1 to 20 carbon atoms, and may be linear or branched.
The arylene group may be substituted, and examples thereof include a phenylene group and a naphthylene group, and examples of the divalent heterocyclic group include pyridine, furan, thiophene, and pyrimidine. The alkylene group represented by R ₂ and R ₂ ' preferably has 1 to 20 carbon atoms, and may be linear or branched. Halogen atoms represented by R ₄ and R ₄ ' include chlorine atom, bromine atom, fluorine atom, etc.
Examples of groups that can be eliminated during the coupling reaction with the oxidation product of the color developing agent include chloro,
Halogen atoms such as bromine and fluorine, -OR', -
OCOR′, −OCONHR′, −OSO ₂ NHR′, −SR′, −
N = NR' and a heterocyclic group having an N atom and bonded to the coupling position via the N atom as used in the art; R' is hydrogen or a substituted or unsubstituted alkyl group, an aryl group; , a heterocyclic group, and preferred substituents for the substituted phenyl group represented by R ₃ and R ₅ include, for example, a halogen atom, an alkyl group, -OR'', -OCOR'', -
SR″, −SOR″, −SO ₂ R″, −SO ₃ H−SO ₃ R″, −
OSO ₂ R″, −COOH, −COOR″, −COR″, −N
(R″) ₂ , −NHCOR″, −NHCONHR″, −
NHSO ₂ R″, −NCONHR″, −CONHSO ₂ R″,
Examples include SO ₂ NHR, -SO ₂ NHCOR'', -CN, -NO ₂ and the like, where R'' represents hydrogen or a group selected from substituted or unsubstituted alkyl groups, aryl groups, and heterocyclic groups.

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[Processing process]

Processing process (38℃) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds Used in each processing step The composition of the treatment liquid was as follows. [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 Anhydrous potassium carbonate 28.85g Sodium bromide 1.3g Trisodium nitrilotriacetic acid (monohydrate)
2.5g Potassium hydroxide 1.0g Add water to make 1, and use potassium hydroxide to
Adjust to PH10.0. 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 Hydroxyamine 1/3 sulfate 1.98g Sulfuric acid 0.74g Anhydrous potassium carbonate 28.85g Anhydrous potassium bicarbonate 3.46g Anhydrous potassium sulfite 5.10g Potassium bromide 1.16g Sodium chloride 0.14g Trisodium nitriloacetate 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, then use ammonia water to pH
Adjust to 6.0. [Fixer composition] Ammonium 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 reversal photosensitive materials will be shown. [Processing process] Processing process (24℃) Processing time 1st development 5 minutes Water washing 4 minutes Exposure Color development 3 minutes Water washing 4 minutes Bleaching 4 minutes Fixing 4 minutes Water washing 10 minutes 1st developer, color development The following processing solutions were used as the bleaching solution, bleaching solution, and fixing solution. [First developer formulation] Anhydrous sodium bisulfite 8.0g Phenidone 0.35g Anhydrous sodium sulfite 37.0g Hydroquinone 5.5g Anhydrous sodium carbonate 28.2g Sodium thiocyanide 1.38g Anhydrous sodium bromide 1.30g Potassium iodide (0.1% aqueous solution) 13.0ml Add water and make it to 1 (PH9.9). [Color developer _{composition] Benzyl alcohol 5.0ml Sodium hexamethanate 2.5g Anhydrous sodium sulfite 1.9g Sodium bromide 1.4g Potassium bromide 0.5g Borax (Na2B4O7 ・ 10H2O )} 39.1g N-ethyl- N-β-methanesulfonamidoethyl-4-amino 3-methylaniline sulfate
Add 5.0g water to make 1, and adjust the pH to 10.30 using sodium hydroxide. [Bleach solution formulation] Anhydrous sodium bromide 43.0g Red blood salt 165.0g Borax (Na ₂ B ₄ O ₇・10H ₂ O 1.2g Add water to make 1. [Fixer formulation] Sodium thiosulfate (5 water) Salt) 200g Anhydrous sodium sulfate 100g Anhydrous disodium phosphate 15g Water was added to prepare 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 described. [Processing process] Processing process (30℃) Processing time Color development 3 minutes 30 seconds Bleach-fixing 1 minute 30 seconds Washing with water 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 color developer (1) above has a color developer composition excluding benzyl alcohol, and the color developer (2) has the following composition:
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] Add 20 ml of glacial acetic acid to make 1, and use sodium acetate to
Adjust to PH3.5~4.0. 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 in the specific examples above) and the following comparative couplers [A], [B], and [C], 10 g of each coupler was used.
were added to a mixture of 2.5 ml of dibutyl phthalate and 20 ml of ethyl acetate, respectively, and the mixture was heated to 60°C to completely dissolve. This solution was mixed with 10% Alkanol B (alkylnaphthalene sulfonate, manufactured by Dupont).
The mixture was mixed with 5 ml of an aqueous solution and 200 ml of a 5% gelatin aqueous solution and emulsified using a colloid mill to prepare 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 seven halogens. Silver compound color photographic materials (sample numbers [1] to [7]) were obtained. Samples of the seven types of silver halide color photographic light-sensitive materials obtained were subjected to wedge exposure according to a conventional method, and then subjected to color development according to the color development process for internal color positives described above as a specific example. 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] In the table, the sensitivity is the sensitivity when using color developer (2) of sample (5) used for comparative coupler [A].
It is shown as a relative value when The structures of comparative couplers [A], [B] and [C] are as shown below. Comparative coupler [A] 6-[α-(2,4-di-tert-amylphenoxy)butanamide], 2,4-di-chloro, 3-
Methylphenol (described in the aforementioned U.S. Pat. No. 2,801,171) Comparative coupler [B] 2-Benzoylamdo, 4-chloro, 5-[α
-(4-butylsulfonamidophenoxy)tetradecanamide]phenol (the above-mentioned JP-A-53-
Comparative coupler [C] 2-benzoylamide, 4-chloro, 5-[α
-{4-(p-Toluenesulfonamide)phenoxy}tetradecanamide]phenol (described in the above-mentioned German Publication No. 3017500) As is clear from the above Table 1, the samples processed by the image forming method of the present invention It can be seen that in a color developer system that has favorable spectral absorption characteristics and does not contain benzyl alcohol, the maximum density of the obtained color image is greater than that of any of the comparative couplers [A], [B], and [C]. . Example 2 Samples 8 to 14 of seven types of photosensitive materials for forming cyan color 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 exposing each obtained image to a xenon fademeter for 200 hours, with the density before exposure being 100. Also,
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 shown in Table 2, comparative coupler [A]
has excellent light resistance, but
Problems remain in heat resistance. Comparative couplers [B] and [C] are couplers with improved heat resistance compared to comparative coupler [A], but they still have problems in light resistance in systems without benzyl alcohol. On the other hand, exemplary coupler [4] according to the present invention,

[9],
[13] and [15] are the above comparative couplers [B] and [C]
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 [21], which is the coupler of the present invention, or the comparative coupler [A] was added to a mixed solution of 25 ml of dibutyl phthalate and 20 ml of ethyl acetate, and the mixture was heated to 60°C to completely dissolve it. . The 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), coated on a cellulose acetate film base, and dried to form a halogen compound with a safe coating film. Samples 15 and 16 of silver oxide 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 carried out in accordance with 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. Further, the sample according to the present invention was a cyan negative image with excellent transparency.

Claims (1)

[Claims] 1. A method for forming a cyan dye image, which comprises causing a cyan coupler represented by the following general formula [] or [] to be present when forming an image on a silver halide color photographic light-sensitive material. General formula [] General formula [] [In the formula, R ₁ and R ₁ ' are an alkoxy group or an aryloxy group, B and B' are an alkylene group,
arylene group or divalent heterocyclic group, R ₂ and R ₂ ' are alkylene groups, R ₃ and R ₅ are alkyl groups, aryl groups, or heterocyclic groups, R ₄ and
R ₄ ' is a hydrogen atom or a halogen atom, Z and
Z' represents a group (excluding a hydrogen atom) that can be eliminated during a coupling reaction with an oxidation product of a color developing agent. n represents 0 or 1, and when n is 0, B represents an arylene group. Further, when B is a phenylene group, R ₁ is bonded to the benzene nucleus at the 2- or 3-position relative to the bonding position of -CONH- or -OR ₂ . ]