JPS6310814B2 - - 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 can be dissolved in a substantially water-insoluble high-boiling organic solvent, optionally with co-solvents, 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. 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 6-[α
-(2,4-di-tert-amylphenoxy)butanamide]-2,4-di-chloro-3-methylphenol, as is clear from the examples below,
Although it has good light resistance, it has drawbacks in heat resistance, and in addition, the color development is highly dependent on benzyl alcohol, and the maximum color development density in a color development processing solution excluding benzyl alcohol is insufficient. In addition, 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 at the time of application or completion was improved by introducing an enoxy group or p-alkylaminosulfonylphenoxy group, but as is clear from the examples below,
The greater the dependence of color development on benzyl alcohol, the more improvement in this point is desired. In addition, the coupler described in German Publication No. 3017497 is an improvement of the color development property of the coupler described in the above-mentioned Japanese Patent Application Laid-open No. 109630/1983 in a color developing solution that excludes benzyl alcohol. Although this coupler has been able to reduce color dependence on alcohol, it is still insufficient.
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. An 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. 2,5- having at least one unsaturated alkylsulfonylamino group having no substituent or an unsaturated alkylaminosulfonyl group having no substituent as a substituent of the group;
This is achieved by using a diacylaminophenol cyan coupler. In a preferred embodiment of the present invention, the 2,5-diacylaminophenol cyan coupler of the present invention is represented by the following general formulas [] and []. General formula [] General formula [] [In the formula, R is an alkylene group having 1 to 20 carbon atoms, R ₁ is an unsaturated alkylsulfonylamino group without a substituent or an unsaturated alkylaminosulfonyl group without a substituent, and R ₂ is an alkyl R ₃ represents a hydrogen atom or a halogen atom, X represents a paraphenylene group or a naphthylene group, Z represents a hydrogen atom or a coupling-off group, and n represents an integer of 1 or 2. ] Furthermore, examples of the group represented by R ₁ in the above general formulas [] and [] include the following groups. _CH2 =CH− _SO2NH−

[Formula] CH ₃ CH=CH−SO ₂ NH− _{CH2 =} CH− _CH2SO2NH− HC≡C− _SO2NH− CH ₃ (CH ₂ ) ₃ CH=CHSO ₂ NH− CH ₃ (CH ₂ ) ₂ CH=CHCH ₂ SO ₂ NH− C ₁₂ H ₂₃ SO ₂ NH− C ₁₈ H ₃₅ SO ₂ NH− C ₁₆ H ₃₁ SO ₂ NH− CH ₂ =CH−CH=CH−SO ₂ NH− CH ₃ (CH ₂ ) ₃ −C≡C−SO _2NH− More specific examples of CH ₂ =CHCH ₂ NHSO ₂ − CH ₂ =CH(CH ₂ ) ₃ NHSO ₂ − C ₁₈ H ₃₅ NHSO ₂ − C ₁₂ H ₂₃ NHSO ₂ − R ₂ include, for example, methyl as the alkyl group. , ethyl, isopropyl, butyl, ter-butyl, dodecyl, pentadecyl, cyclohexyl, etc.; examples of the aryl group include phenyl, naphthalene, etc.; examples of the heterocyclic residue include, for example, a furan group. Further, as substituents for each of these groups, for example, a halogen atom (each atom such as chlorine, bromine, fluorine, etc.), a nitro group, a hydroxy group, a carboxy group, an amino group,
Sulfonyl group, cyano group, alkoxy group, aryloxy group, arylthio group, acylamino group,
Examples include carbamoyl group, ester group, acyl group, acyloxy group, sulfonamide group, sulfamoyl group, sulfonyl group, sulfoxy group, oxysulfonyl group, and the like. Also, a paraphenylene group as the group of the above-mentioned X,
Each group of the naphthylene group may be substituted with the following substituents. For example, alkyl groups (e.g. methyl group, ethyl group, isobutyl group, dodecyl group,
ter-amyl group, cyclohexyl group, pentadecyl group, etc.), alkenyl group (e.g. allyl group, etc.), aryl group, heterocyclic residue, halogen atom (e.g. chlorine, bromine, fluorine, etc. atoms), nitro group , hydroxy group, carboxy group, amino group, sulfo group, alkoxy group, aryloxy group, arylthio group, acylamino group, carbamoyl group,
Ester group, acyl group, acyloxy group, sulfonamide group, sulfamoyl group, sulfonyl group,
These are various groups such as morpholino group. Further, R is an alkylene group having 1 to 20 carbon atoms, and 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, Publication No. 36894, Publication No. 36894, Publication No. 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. 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, and has good transparency. The color emulsion according to the present invention containing the above 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, color development without benzyl alcohol. It has properties such as a fast dye formation rate in the processing solution and a high color density. However, U.S. Pat.
Also US Patent No. 3998642, US Patent No. 3839044
The coupler of the present invention is not even suggested in JP-A No. 53-109630, etc., and as will be clear from the examples described later, the effect exhibited by the coupler of the present invention is completely surprising. Something I should have done happened. 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 heat resistance. Next, typical examples of the couplers of the present invention will be given. The couplers of the present invention used in the present invention are as follows:
It is not limited to this.

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[Processing process]

Processing process (33℃) 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 Can be used in the above processing steps The composition of the treatment liquid 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 Nitrilo sulfate Trisodium 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 adjust to PH6.0 using aqueous ammonia. [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 to process internal color positive light-sensitive materials will be shown. [Processing process] Processing process (30℃) Processing time Color development: 3 minutes and 30 seconds Bleach-fixing: 1 minute and 30 seconds Water washing: 2 minutes Stabilization: 1 minute Can be used in the above processing steps The composition of each treatment liquid 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) mentioned above 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, and use ammonia water to adjust the pH.
Adjust to 6.5. [Stabilizing liquid composition] Add 20 ml of glacial acetic acid to make 1, and use sodium acetate to
Adjust to PH3.5~4.0. 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], [C], and [D], each coupler was 10 g of each 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 % silver bromide) emulsion, coated on polyethylene-coated paper and dried to form seven types with stable coatings. Silver halide 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. The experiment was conducted using two types of color developing solutions: 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 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 (as described in US Pat. No. 2,801,171) Comparative coupler [B] 2-benzamide-5-[α-(4-butylsulfonylaminophenoxy)tetradecanamide]
Phenol (from the above-mentioned JP-A-53-109630) Comparative coupler [C] 2-benzamide-5-{α-[4-(p-dodecylbenzenesulfonamide)phenoxy]butanamide}phenol (West German Published Patent Application No. 3017497) Comparative coupler [D] 2-benzamido-5-{α-[3-(N-butanesulfonyl-N-benzylaminophenoxy)]
Tetradecanamide}phenol (released in West Germany)
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 they can also be obtained in a color developing solution system that does not contain benzyl alcohol. The maximum density of the color image was compared with the couplers [A], [B], [C], [D]
It can be seen that it is larger than both. 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 the table, light resistance is determined by the residual density after exposing each image to a xenon fademeter for 200 hours.
The concentration before exposure was expressed as 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 at 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. In addition, 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 [1], [13],
[16] has heat resistance equivalent to that of the above-mentioned comparative coupler [B], and an improvement in light resistance is recognized. Example 3 10 g of the exemplary coupler [6] or the comparative coupler [A] of the present invention 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. . 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), coated on a cellulose acetate film base, and dried to form a halogen compound with a stable coating film. Samples 13 and 14 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.

[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 (9) 2.0g Make up to 1 with water. A sample obtained by coating a high-sensitivity silver iodobromide emulsion on a subbed polyethylene terephthalate film was exposed to light using a conventional method, and then developed for 30 minutes at 24°C with the external color developer described above. . 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)

[Claims] 1 Silver halide color photographic light-sensitive material with 2,5-
In a method of forming a cyan dye image by image processing in the presence of a diacylaminophenol cyan coupler, the substituent of the acylamino group at the 2- or 5-position of the phenol ring of the cyan coupler does not have at least one substituent. 1. A method for forming a cyan dye image, comprising an unsaturated alkylsulfonylamino group or an unsaturated alkylaminosulfonyl group having no substituent.