JPH05695B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for forming a color photographic image using a silver halide color photographic light-sensitive material, and more particularly to a method for rapidly and stably forming a stain-free, high-quality dye image. Generally, in order to process a silver halide color photographic light-sensitive material to form a color photographic image, the light-sensitive material is imagewise exposed, developed with a color photographic developer containing an aromatic primary amine color developer, and then processed to form a color photographic image. A method is used in which a developer is added at the same time as silver oxide is reduced to silver, and the oxidation product of the developer formed is combined with a coupler to form an image-like dye corresponding to the distribution of developed silver. It is being The above color image forming method includes, for example, imagewise exposing a silver halide color photographic light-sensitive material containing a non-diffusible coupler, processing it with a color photographic developer, and further desilvering and fixing to form a color negative image. There is an internal development method in which the silver halide color photographic light-sensitive material is imagewise exposed, black and white first development is carried out, and then the remaining silver halide emulsion is uniformly exposed, and the internal development method or external development method is used. There is a method in which a reversal color photographic image is formed by processing with a color photographic developer, followed by desilvering and fixing.Furthermore, the above method is applied to a multicolor reflective photographic material in which a color photographic emulsion layer is provided on an opaque support. There is a method of printing a film having a color negative image formed thereon, developing a color photograph, and desilvering and fixing it to form a color positive image. In all of these various color image forming methods, an active p-phenylenediamine developer is used. Conventionally, when a color photographic image is formed by processing a silver halide color photographic light-sensitive material with such a p-phenylenediamine developer, all the silver halide grains exposed to light and forming a latent image are effectively converted into silver and pigments. Instead, a considerable amount of the silver halide that formed the latent image is dissolved in the fixing solution and discarded without being effectively utilized. If silver halide grains are effectively converted into silver and dyes without waste, excellent color images with higher contrast can be obtained, and the amount of silver can be reduced accordingly, making it possible to make photosensitive materials thinner. Therefore, many advantages should be obtained, such as rapid development processing and the ability to obtain high-resolution color images. These advantages have become more strongly desired in recent years as automatic processors have been used to rapidly process large quantities. In response to these demands, p-phenylenediamine is capable of forming reduced silver more efficiently when developing silver halide on which a latent image has been formed, compared to conventional p-phenylenediamine-based developers. A system developer is disclosed. That is, Japanese Patent Application Publication No. 1973-
No. 64932, No. 48-64933, Special Publication No. 54-16860,
No. 53-13972, JP-A No. 51-95849, No. 51-
These are described in specifications such as No. 147322, No. 52-76032, and No. 53-31133. The developer described in the above specification has much better permeability and adsorption to the silver halide emulsion layer than conventional p-phenylenediamine developers, and has a high color development speed. Further, when the latent silver halide image obtained by imagewise exposure of a silver halide photographic light-sensitive material is color developed, reduced silver can be efficiently formed, and there is an advantage that no wasted silver halide is left behind. be. Furthermore, when a latent image is color-developed, the ratio of the density of the developed silver to the density of the dye simultaneously formed is greater than that obtained with conventional developers. On the other hand, after developing a silver halide color photographic light-sensitive material with a color developing solution containing a p-phenylenediamine developer, a bleaching treatment is usually performed to remove developed silver and undeveloped silver halide remaining in the light-sensitive material. A fixing process or a one-bath bleach-fixing process is carried out. Particularly in recent years, for the purpose of speeding up or simplifying development, it is common to immediately carry out a bleaching process or a one-bath bleach-fixing process. As the main component of these bleaching solutions and bleach-fixing solutions, aminopolycarboxylic acid iron salts, typified by low-pollution EDTAFe salts, are used, although their oxidizing power is weaker than that of conventionally used red blood salts. Further, such color development processing is carried out continuously using an automatic processor in order to quickly produce a large quantity of color films or color prints. Therefore, the color developing solution that has adhered to the color photographic material or its surface is brought into the bleaching solution or bleach-fixing solution and accumulated therein. Color developers added to color developing solutions that are currently in practical use, such as 4-amino-3-methyl-
N-Ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate and 4-amino-3-methyl-N-ethyl-N-hydroxyethylaniline sulfate were compared even if they accumulated in the bleach solution or bleach-fix solution. It is oxidized by the oxidizing agent in a relatively short period of time, causing almost no problem in terms of photographic properties. However, these color developers cannot be said to have very good color development properties. On the other hand, in color processing using the above-mentioned color developer with excellent color forming properties, the color developer accumulated in the bleach solution or bleach-fix solution tends to be less susceptible to oxidation and remain for a long period of time. Continuous processing of color photosensitive materials under such conditions has the serious drawback of staining. The reason why this stain is likely to occur is largely related to the susceptibility to oxidation as mentioned above.In addition, these color developing agents are present in large amounts in the gelatin film of color photographic light-sensitive materials or in high boiling point solvents containing couplers. It is thought that this is closely related to the fact that it has a tendency to be easily contained, and that a large amount is brought into the oxidizing solution bath after color development processing. Therefore, the actual situation is that it cannot be applied to a direct oxidizing solution bath treatment step after development. Such staining can be prevented by washing with water or stopping the development and bleaching or bleach-fixing, but this goes against the demands of the times to omit steps, shorten time, and reduce pollution. The best means is to lower the pH of the bleach or bleach-fix solution so that it has the ability to stop development. This simultaneously improves the ability to oxidize silver and has the possibility of speeding up the process. However, there are other problems with lowering the PH. That is, in the case of a cyan coupler, the cyan dye produced during color development becomes a colorless leuco dye during the bleaching process. This is considered to be due to the fact that when a weak oxidizing agent is used, proton addition of hydrogen ions takes priority over the rate at which the dye is oxidized. Therefore, although patents and literature suggest that conventional bleaching solutions and bleach-fixing solutions that use organic acid iron salts as oxidizing agents can be processed even in highly acidic conditions, in practice, conditions are set at a pH of 6.0 or higher. The reality is that Accordingly, a first object of the present invention is to provide a method for forming stain-free color images with high sensitivity. A second object is to provide a method for forming a good color image with excellent color reproducibility. A third object is to provide a color image forming method that is highly suitable for high temperature and rapid processing. The fourth object is to provide a method for forming a color image that achieves low pollution by reducing or removing benzyl alcohol, which is a development accelerator normally contained in color developing solutions. These objects are achieved by imagewise exposure of a multilayer silver halide color photographic light-sensitive material having a photosensitive silver halide emulsion layer containing a cyan coupler represented by the following general formula (). It has been found that good color photographic images can be obtained by processing with a developer containing a color developer and then directly processing with a bleaching solution having a pH of 2 to 5.5. General formula () In the formula, R ₁ and R ₈ represent an alkyl group, an alkylsulfamoyl group, an alkylsulfamoylamino group, or an alkylsulfonamido group, each of which may be substituted, and R ₂ is an acyl group or a carbamoyl group. (each may be substituted), R ₃ represents a hydrogen atom or a halogen atom, R ₇ represents a hydrogen atom or an alkyl group, Z represents a hydrogen atom or a coupling-off group (the coupling-off group shown by Z are well known to those skilled in the art. Such groups determine the equivalence of the coupler (i.e. whether it is 2-equivalent or 4-equivalent);
The reactivity of the coupler is modified and the coupler in the photographic element is applied to the layer or other layers to inhibit development, inhibit bleaching, and
It can also have an advantageous effect by performing functions such as bleach enhancement and color correction. ), and m represents an integer from 1 to 3. General formula () In the formula, R ₁₁ represents a hydrogen atom, an alkyl group (preferably has 1 to 4 carbon atoms, and may be substituted), or R ₁₂ , and R ₁₂ is -(R ₄ O)m-(R ₅ O) represents n-R ₆ (R ₄ and R ₅ represent an alkylene group (preferably has 1 to 4 carbon atoms, may be a straight chain or branched chain, and may be substituted), and R ₄ and R ₅ may be the same or the same at the same time. m and n are each 0 or an integer from 1 to 4, and cannot be 0 at the same time. R ₆ represents an alkyl group), R ₁₃
represents a hydrogen atom or an alkyl group (preferably having 1 to 4 carbon atoms), and each group may be substituted. Furthermore, the alkyl group represented by R ₁ in the general formula () may be either saturated or unsaturated, and may be linear, branched, or cyclic. Particularly preferred are, for example, methyl, ethyl, isobutyl, t-butyl, dodecyl, octadecyl, cyclobutyl, and cyclohexyl. Furthermore, the aryl group represented by R ₁ includes phenyl and naphthyl. And they may have the same substituent or different substituents at the same time. Examples of substituents introduced into these alkyl groups and aryl groups include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino,
Examples include groups such as sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino. R ₂ is an acyl group represented by COR ₄ or a carbamoyl group represented by CONHR ₁₄ , and R ₁₄ is an alkyl group, an aryl group, or a heterocycle. More specific examples of _R14 include alkyl groups such as methyl, ethyl, isopropyl, butyl, ter-butyl, dodecyl, pentadecyl, and cyclohexyl; aryl groups such as phenyl and naphthalene; Examples of the heterocyclic residue include a furan group. Furthermore, examples of substituents to be substituted on these groups include halogen atoms (chlorine, bromine, fluorine, etc.), nitro groups,
Hydroxy group, carboxy group, amino group, 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, Examples include sulfoxy group and oxysulfonyl group. 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. 50-1117422, 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. Next, specific examples of the compound represented by the general formula () will be shown, but the invention is not limited thereto.

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〔Processing method〕

Process Time color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds water washing 2 minutes Temperature 30℃ [Processing solution composition] (Color developer) Potassium carbonate 30g Potassium sulfite 2g Potassium bromide 0.6g Hydroxylamine sulfate 4g Color developing agent 0.01 Add molar water to 1, and adjust the pH to 10.20 with KOH. (Bleach-fix solution) Iron ammonium ethylenediaminetetraacetate
60g Diammonium ethylenediaminetetraacetate
5g Sodium sulfite 10g Ammonium thiosulfate 100g Said color developer 300ml Add water and adjust to Hz4-7.5 with aqueous ammonia or acetic acid.

〔Processing method〕

Process Timed color development Bleaching for 3 minutes and 15 seconds Fixing for 3 minutes and 15 seconds Washing with water for 4 minutes and 20 seconds Stable for 4 minutes and 20 seconds 1 minute and 05 seconds Temperature 38℃ [Processing solution composition] (Color developer) Sodium sulfite 5g Hydroxylamine sulfate 2g Carbonic acid Potassium 30g Sodium bromide 1.2g Trisodium nitrilotriacetate 2.0g Color developing agent 0.01 mol Add water to make 1, and adjust the pH to 10.00 with potassium hydroxide or sulfuric acid. (Bleach solution) Iron ammonium ethylenediaminetetraacetate
100g Diammonium ethylenediaminetetraacetate
10g Ammonium bromide 150g Add water to make 1, and adjust the pH to 4-7 with aqueous ammonia or acetic acid. (Fixer) Ammonium thiosulfate 100g Sodium sulfite 10g Finish with water. (Stabilizer) 35% formalin 5ml Dimethylsiloxane/ethylene oxide adduct
Finish with 0.5g water.

[Table] In Table 2, "Desilvering property" is marked with ○, which means that no metallic silver remains in the photosensitive material. △ means that some metallic silver remains. × represents a state in which metallic silver remains. As is clear from Table 2, by combining the coupler of the present invention, the active ingredient, and the pH of the bleaching bath, rapid and stable processing is possible without staining, dye fading, and desilvering failure. It turns out that there is something. Example 3 Using a silver halide color photographic light-sensitive material prepared in the same manner as in Example 1 using the silver halide color photographic light-sensitive material prepared in Example 1 and exemplary couplers -22 and -26, a bleach-fixing solution was prepared. The experiments and evaluations were carried out in the same manner as in Example 1, except for the changes shown in Table 3. The results are shown in Table 3.

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[Table] From Table 3, when the pH of the bleach-fix solution is higher than 5.5, when the couplers of the present invention are used, the minimum density (fog) increases, making them impractical.
On the other hand, when the pH is lower than 2.0, no increase in fog is observed, but the maximum concentration is low and the increase due to reoxidation is large, making it unsuitable for practical use. However, when the coupler according to the present invention is developed with the color developing agent according to the present invention and the pH of the bleach-fix solution is in the range of 2.0 to 5.5, there is no fogging, the maximum density is high, and there is no increase in reoxidation. I understand that. Example 4 A silver halide color photographic light-sensitive material prepared in the same manner as in Example 2 using the silver halide color photographic light-sensitive material prepared in Example 2 and exemplary couplers -22 and -26 was used, and a bleaching solution was prepared according to Table 4. Experiments and evaluations were carried out in the same manner as in Example 2, except for the changes shown in Figure 2. The results are shown in the table below.
4.

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[Table] Table 4 also reproduces the development in Table 3, and when the pH of the bleaching solution is higher than 5.5, the minimum density (fog) increases in both cases when the coupler of the present invention is used, while the pH increases. When the value was lower than 2.0, no increase in fog was observed, but the maximum concentration was low and the increase due to reoxidation was large. Then, when the coupler according to the present invention is developed with the color developing agent according to the present invention, and the pH of the bleaching solution is in the range of 2.0 to 5.5,
There was no fog, the maximum density was high, there was no increase in reoxidation, and the desilvering property was good. However, it turns out that the comparative example has some drawbacks.

Claims (1)

[Scope of Claims] 1 After imagewise exposure of a multilayer silver halide color photographic light-sensitive material having a light-sensitive silver halide emulsion layer containing a cyan coupler represented by the following general formula () on a support, Processed with a developer containing the color photographic developer shown in parentheses, then PH2~
A method for forming a color photographic image, characterized by processing with a bleaching solution of 5.5. General formula () (wherein R ₁ and R ₈ represent an alkyl group, an alkylsulfamoyl group, an alkylsulfamoylamino group or an alkylsulfonamide group,
R ₂ represents an acyl group or a carbamoyl group,
R ₃ represents a hydrogen atom or a halogen atom, R ₇
represents a hydrogen atom or an alkyl group, and Z represents a hydrogen atom or a coupling-off group. ) General formula () [In the formula, R ₁₁ is a hydrogen atom, an alkyl group, or R ₁₂
, R ₁₂ represents -(R ₄ O)m-(R ₅ O)n-R ₆ (R ₄ and R ₅ represent an alkylene group,
R ₄ and R ₅ may be the same at the same time. m,
Each n is 0 or an integer from 1 to 4, and cannot be 0 at the same time. R ₆ represents an alkyl group. ), R ₁₃ represents a hydrogen atom or an alkyl group. ]