JPH0526183B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a dye image, and more particularly, the present invention relates to a method for forming a dye image, and more specifically, a method for forming a dye image, in which a silver halide photographic light-sensitive material that has been imagewise exposed is subjected to color development treatment, bleaching treatment, and fixing treatment separately. The present invention relates to a method for forming a dye image. Prior Art and Problems Therein Generally, a silver halide color photographic light-sensitive material consists of a blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a cyan light-sensitive silver halide emulsion layer on a support. It has a red-sensitive silver halide emulsion layer containing a coupler, and after being imagewise exposed, it is processed with a color developing solution containing a p-phenylenediamine derivative as a color developing agent to form a dye image and silver. An image is formed and then bleaching and fixing processes remove the silver image, leaving the dye image. In this case, from the viewpoint of reducing the number of baths and speeding up processing, it is well known in the art that bleaching and fixing are carried out in one bath as a bleach-fixing process. In the bleaching process, the silver image is oxidized by an oxidizing agent, and it usually forms an association with halogen ions and remains as silver halide in the silver halide color photographic light-sensitive material.
In the subsequent fixing process, this silver halide becomes a soluble silver complex salt with a silver halide solvent such as thiosulfate and is eluted and removed from the silver halide color photographic light-sensitive material. Soluble silver complex salts are eluted and accumulated in the processing solution of the bath. Oxidizing agents used in bleaching include red blood salts, dichromates, and iron() polycarboxylic acid complexes represented by iron()EDTA complexes. Red blood salts and dichromates are iron
It has a higher bleaching rate than EDTA complex salts and has a high ability to oxidize the leuco bodies formed during the color development process to the final dye. However, in recent years, from the perspective of environmental conservation, it is necessary to recover these red blood salts and dichromates during waste water treatment of bleaching solutions and subsequent washing solutions, and this treatment has become quite difficult and is no longer practical. It's becoming less and less of a target. Therefore, in recent years, iron () polycarboxylic acid complex salts, which cause less environmental pollution, have been widely used.However, iron () polycarboxylic acid complex salts have a relatively weak oxidizing power, so they have the disadvantage that the bleaching process takes a long time. It was hot. By the way, as mentioned above, there are cases where the desilvering process is divided into a bleaching process and a fixing process, and there are cases where a bleach-fixing process is performed using a single processing solution. In general, silver halide color photographic light-sensitive materials with a high silver iodide content (for example, 3 mol% or more) are
When processing with a bleach-fix solution using EDTA complex salts as an oxidizing agent, desilvering often fails, so the bleach solution and fix solution are used separately for processing.
In addition, iron () reduced by oxidation reaction
Some attempts have been made to oxidize DETA complex salts to the original iron()DETA complex salts and regenerate and use fatigued bleaching solutions or fatigued bleach-fixing solutions. In this case, when using a bleach-fix solution, the silver concentration in the solution increases as the solution is reused, and from the viewpoint of saving silver resources, it is necessary to reduce the amount of silver accumulated in the exhausted bleach-fix solution. Parts are removed and recovered. Methods for recovering silver from such a bleach-fix solution include (1) a method of adding a chemical that forms a poorly soluble silver salt, and (2) a method of replacing silver by contacting it with a metal such as iron that has a greater tendency to ionize than silver. , (3) electrolytic method, and (4) method using ion exchange resin have been proposed.
However, with these methods, after silver is recovered, it becomes impossible to regenerate it as a bleach-fix solution at all, and most of the iron()EDTA complex salts are reduced to iron()EDTA complex salts. It also has the drawback of removing a considerable amount of useful thiosulfates and iron complexes. Even in the particularly preferred electrolytic method, it is difficult to say that it is industrially sufficient to efficiently recover silver and regenerate the bleach-fix solution at the same time. From this point of view, in some cases, even if bleach-fixing can be used as a treatment process, the bleaching solution and fixing solution are deliberately separated from the viewpoint of recycling the processing solution and saving silver resources. There are many. By the way, as mentioned above, when a silver halide color photographic light-sensitive material having a relatively high silver iodide composition is processed with a bleach-fix solution using an iron ()EDTA complex salt as an oxidizing agent, it is separated into a bleach solution and a fix solution. On the other hand, in silver halide color photographic materials that have a relatively low silver iodide ratio or do not contain any silver iodide, iron()EDTA It has been found that desilvering defects are more likely to occur when the bleach and fix solutions are used separately, compared to when the bleach-fix solution uses complex salts as the oxidizing agent. Although it is unclear why this phenomenon occurs, it is thought to be due to the difference in the effects of iodide ions and thiosulfate ions on the bleaching rate. Various methods for accelerating the bleaching speed have been known for a long time.For example, ``The Theory of
“The Photographic Process”
theory of the Photographic Process”), No. 4
Edition, Macmillan Pub.Co.
Published by Ino.), p447-453, Fundamentals of Photographic Engineering, edited by the Photographic Society of Japan, p356-357, "Photographic Processing" by RJCox, published by Academic Fres ( Published by Academi Press)
It is known to add compounds such as those described on pages 223 to 238 to a bleach solution or a bleach-fix solution. However, these conventionally known bleach accelerators do not have sufficient effect, are not stable in bleaching solutions, or their concentration in bleaching solutions rapidly decreases when subjected to long-term running processing.
Alternatively, silver halide remains in the photographic light-sensitive material even after all processing, impairing the photographic performance such as the storage stability of the light-sensitive material. It's hard to say that there are. OBJECT OF THE INVENTION The object of the present invention is to stably promote desilvering without impairing the photographic performance of silver halide photographic materials, and to form good dye images by accelerating the bleaching speed. The goal is to provide a way to do so. The object of the present invention is to process a silver halide photographic material that has been imagewise exposed through a color development process→bleaching process→
In the method of forming a dye image by performing each fixing process in this order, the color development process is performed in step 4,
The bleaching treatment is carried out in the presence of a 4'-diaminostilbene water-soluble fluorescent brightener, and the bleaching treatment is carried out in the presence of an iron() polycarboxylic acid complex salt and in the substantial absence of a fixing agent. This can be achieved by a method for forming a dye image. As the 4,4'-diaminostilbene water-soluble fluorescent brightener used in the present invention, conventionally known ones can be used. Suitable examples include compounds represented by the following general formula []. General formula [] In the formula, X ₁ and X ₂ are each

[Formula] or represents an R ₃ -CO- group. Here, R ₁ , R ₂ and R ₃ are each a hydroxy group, a halogen atom (chlorine, bromine, etc.), a morpholino group, an alkoxyl group (such as a methoxy group,
ethoxy group, methoxyethoxy group, etc.), aryloxy group (e.g., phenoxy group, p-sulfophenoxy group, etc.), alkyl group (e.g., methyl group, ethyl group, etc.), aryl group (e.g., phenyl group,
methoxyphenyl group, etc.), amino group, alkylamino group, (e.g. methylamino group, ethylamino group, propylamino group, dimethylamino group, cyclohexylamino group, β-hydroxyethylamino group, di(β-hydroxyethyl) Amino group, β
-sulfoethylamino group, N-(β-sulfoethyl)-N'-methylamino group, N-(β-hydroxyethyl-N'-methylamino group, etc.), or arylamino group (e.g., anilino group, o- ,m
-, p-sulfoanilino group, o-, m-, p-chloroanilino group, o-, m-, p-toluidino group, o-, m-, p-carboxyanilino group, o
-, m-, p-hydroxyanilino group, sulfonaphthylamino group, o-, m-, p-aminoanilino group, o-, m-, p-anisidino group, etc.). M represents a hydrogen atom or a cation. Specific examples of the 4,4'-diaminostilbendisulfonic acid derivative represented by the general formula [] include the following. In order to obtain the effects of the present invention, the 4,4'-diaminostilbene water-soluble fluorescent whitening agent according to the present invention (hereinafter referred to as the fluorescent whitening agent according to the present invention) must be present during color development processing. It is essential, and if it is added only to the solution used for bleaching treatment (hereinafter referred to as bleaching solution), the effects of the present invention cannot be obtained at all. Although the fluorescent whitening agent according to the present invention may be added in advance to the silver halide emulsion layer of the silver halide photographic light-sensitive material according to the present invention, it is preferable to add it to the solution used for color development processing (hereinafter referred to as color developer). ). Alternatively, it may be added to the silver halide photographic light-sensitive material according to the present invention and also to the color developing solution. When added to this silver halide photographic light-sensitive material, it is preferably in the range of 0.01 to 0.5 g, more preferably 0.02 to 0.3 g, per 1 m ² of the light-sensitive material. The addition position may be any of the silver halide emulsion layer, non-emulsion layer, subbing layer, etc., but preferably the non-emulsion layer. When added to a color developer, 0.1 to 10g, or even 0.3g per color developer.
A range of ~5g is preferred. The iron() polycarboxylic acid complex salt present in the bleaching process according to the invention is usually added to the bleaching solution. As the iron() polycarboxylic acid complex salt according to the present invention, conventionally known ones can be used. In particular, iron()aminopolycarboxylic acid complex salts are useful in the present invention. Iron() aminopolycarboxylic acid complex salts are complex compounds consisting of iron() ions and aminopolycarboxylic acid ions, and these complex compounds are usually used as sodium salts, potassium salts, or ammonium salts. Examples of aminopolycarboxylic acids include ethylenediaminetetraacetic acid (EDTA),
Diethylenetriaminepentaacetic acid, methyliminodiacetic acid, N-methyl-N-hydroxyethyliminodiacetic acid, ethyliminodiacetic acid, ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid , cyclohexanediaminetetraacetic acid, ethyl etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, and phenylenediaminetetraacetic acid. The color developing agent contained in the color developer according to the present invention is preferably a p-phenylenediamine derivative. For example, N,N-diethyl-p-phenylenediamine, N-methyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, 2-amino-5-(N-ethyl-N-dodecyl) Aminotoluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-
N,N-diethylaniline, 4-amino-N-
Examples include (β-methoxyethyl)-N-ethyl-3-methylaniline, N,N-diethyl-3-(β-methanesulfonamido)ethyl-4-amino-aniline, and the like. The silver halide photographic material according to the present invention may contain these color developing agents in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor. The color developing agent breaker is a compound that can produce a color developing agent under alkaline conditions, and includes a Schiff base type breaker with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative breaker, a phosphoric acid amide derivative breaker, Examples include Shugar amine reactant breaker and urethane type breaker. Breakers for these aromatic primary amine color developing agents are disclosed in, for example, U.S. Pat.
2695234, British Patent No. 3719492, British Patent No. 803783, Japanese Unexamined Patent Publications No. 53-135628 and 54-79035, Research Disclosure Magazine 15159
No. 12146, No. 13924. In this case, the color developing solution used to color develop the silver halide photographic light-sensitive material containing the color developing agent or its breaker is a conventionally known alkaline processing solution (so-called activation bath or activator solution). ). These aromatic primary amine color developing agents or their breaker must be added in an amount that will provide sufficient color development during color development processing.
This amount varies considerably depending on the type of silver halide photographic light-sensitive material, but is generally between 0.1 mol and 5 mol per mol of photosensitive silver halide, preferably,
It is used in a range of 0.5 mol to 3 mol. These color developing agents or their breaker may be used alone or in combination. In order to incorporate the above compound into a photographic light-sensitive material, it can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc., and added. It can be added as an emulsified dispersion using a high-boiling organic solvent or by impregnating a latex polymer as described in Research Disclosure No. 14850. The color developing solution used in the present invention contains the above p-
In addition to phenylenediamine color developing agents, sodium hydroxide, potassium hydroxide, potassium carbonate,
Alkaline agents such as trisodium phosphate, PH buffers such as boric acid and acetic acid, thioethers, 1-aryl-
Known development accelerators such as 3-pyrazolidones, N-methyl-p-aminophenols, and polyalkylene glycol; various organic agents such as benzyl alcohol, ethanol, butanol, ethylene glycol, diethylene glycol, acetone, and N,N-dimethylformamide; Solvents, potassium bromide, development inhibitors such as nitrobenzimidazole, preservatives such as sulfites, hydroxylamine, glycose, alkanols, amines, polyphosphoric acid compounds,
A hardening and softening agent such as nitrilotriacetic acid is included as necessary. PH of color developer used in the present invention
is between 9 and 12, preferably between 9.5 and 11. In addition to the above-mentioned oxidizing agents, the bleaching solution used in the present invention includes pH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, polyaminocarboxylic acids or their salts, alkylamines, and polyethylene oxides. Those known to be added to ordinary bleaching solutions, such as bleaching agents, can be added as appropriate. It is preferable to add a water-soluble halide to the bleaching solution used in the present invention, and water-soluble bromides such as potassium bromide and ammonium bromide are particularly preferable. The amount of iron(), polycarboxylic acid complex salt used in the bleaching solution used in the present invention is 20% per bleaching solution.
g to 120 g, preferably 40 g to 100 g.
The amount of water-soluble halide used is 10g to 150g per water-soluble bromide, preferably 30g to 150g per water-soluble bromide.
It is in the range of 100g to 100g. In addition, known bleaching accelerators may be appropriately used in the bleaching solution used in the present invention as long as they do not impair the effects of the present invention. As the fixing solution used in the fixing step following the bleaching step according to the present invention, any conventionally known fixing solution can be used. The most common fixatives are thiosulfates such as sodium thiosulfate, ammonium thiosulfate, and potassium thiosulfate, and may also contain stabilizers such as sulfites and isomeric bisulfites, PH buffers, etc. I can do it. The preferred bleaching solution has a pH of 5 to 7. In the method of forming a dye image of the present invention,
The three processing steps of color development processing, bleaching processing, and fixing processing are essential, but if necessary, washing with water,
Processing steps such as stabilization and stopping can be performed before, during, or after the three processing steps described above. In particular, it is preferable to provide a washing step between the bleaching step and the fixing step. The following examples can be given as preferable treatment steps in the present invention. (1) Color development processing → Water washing → Bleaching processing → Water washing → Fixing processing → Water washing (2) Color development processing → Water washing → Bleaching processing → Water washing → Fixing processing → Preliminary washing → Water washing (3) Color development processing → Water washing → Bleaching processing → Water washing → Fixing → Water washing → Stabilization (4) Color development processing → Water washing → Bleaching → Water washing → Fixing → Water washing → Stabilization → Water washing (5) Color development processing → Bleaching → Water washing → Fixing processing →
Water Washing In addition to the above-mentioned treatments, in order to perform reversal development using a surface latent image type emulsion, treatments such as a first black and white development process, water washing, and light fogging may also be performed prior to the color development process. On the other hand, when an internal latent image emulsion is used, the color development process also includes color development that performs fog development. The temperature at which the silver halide color photographic material relating to the present invention is processed is usually in the range of 10 to 60°C,
Preferably it is in the range of 25 to 45°C. The bleaching liquid used in the invention is particularly suitable for reuse, especially in the case of long-term running treatments. In order to restore the oxidizing power, the fatigue bleaching solution sufficiently oxidizes the iron () polycarboxylic acid complex salt to the iron () polycarboxylic acid complex salt by blowing air or electrolytically regenerating it, and then removes water-soluble bromide and other necessary regenerating agents. It can also be added and reused. The light-sensitive silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention may be either a normal negative surface latent image type emulsion or an internal latent image type emulsion. As a photosensitive halogenated emulsion,
Any one of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide is used, but in order to maximize the effects of the present invention, the silver iodide content is small. is preferable. Particularly preferred are emulsions containing no silver iodide, but containing silver chloride, silver chlorobromide, or silver bromide. These silver halides may be produced by any of the neutral method, ammonia method, and acidic method, and may be produced by any method such as simultaneous mixing method, forward mixing method, back mixing method, convergence method, etc. Silver halide grains produced by the method can also be applied to the present invention. Furthermore, the crystal habit of the silver halide grains according to the present invention may be (100) plane, (111) plane, or a mixture thereof, and the silver halide grains may have phase interfaces with different halogen compositions inside. It may be something that you do. Regarding the grain size of the silver halide grains, when the average grain size is 0.6 μm or more, and when the silver halide emulsion is close to the support, the silver halide emulsion containing silver halide grains having a relatively large grain size is The effects of the present invention are particularly well exhibited when the material is a silver photographic material. Further, the effects of the present invention are fully exhibited when the amount of silver contained in a single photosensitive silver halide emulsion layer is 0.5 g/m ² or less. When these silver halide emulsions are used as surface latent image emulsions, noble metal salts such as ruthenium, rhodium, iridium, gold, platinum (for example, ammonium chloroparadate, potassium chloroplatinate, potassium chloroparadite, potassium active gelatin, sulfur sensitization with unstable sulfur compounds (e.g. sodium thiosulfate), selenium sensitization with selenium compounds, or stannous salts, polyamines and under low pAg conditions. Chemical sensitization such as reduction sensitization can be performed. On the other hand, when silver halide emulsions are used as internal latent enhancement emulsions, conversion emulsions, internal chemical sensitization (sulfur sensitization, noble metal sensitization) emulsions, emulsions in which polyvalent metal ions are doped inside silver halide grains are used. Further, known internal latent image type emulsions such as layered emulsions having phase interfaces with different halogen compositions inside silver halide grains can be used. The various emulsions described above can be optically sensitized using various optical sensitizers to impart photosensitivity to desired spectral regions. Examples of optical sensitizers that can be used at this time include US Pat.
No. 1939201, No. 2072908, No. 2739149, No. 2213995, No. 2493748, No. 2519001,
West German Patent No. 929080 and British Patent No. 505979
The cyanine dyes, merocyanine dyes, or composite cyanine dyes described in each specification of the No. 1 can be used alone or in combination of two or more.
These various sensitizers are used for purposes other than their original purpose, such as preventing fog, preventing deterioration of photographic performance during storage of silver halide color photographic materials, and adjusting development (for example, gradation control, etc.). It can also be used for. The constituent layers of the silver halide color photographic light-sensitive material according to the present invention may optionally contain known sensitizers such as thioether compounds, quaternary ammonium salt compounds, or polyalkylene oxide compounds, triazoles, imidazoles, Stabilizers such as asaindenes, benzothiazoliums, nucleic acid decomposition products (eg, adenine, guanine, etc.), zinc compounds, cadmium compounds, and mercaptans can be used within the range that does not impair the effects of the present invention. The binder used in the constituent layers of the silver halide color photographic light-sensitive material according to the present invention is most commonly gelatin such as alkali-treated gelatin or acid-treated gelatin. Derivative gelatin such as phenylcarbamoyl gelatin, albumin, agar, gum arabic, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate,
Polyacrylamide, polyvinyl alcohol, polyvinylimidazole, polyvinylpyrrolidone and copolymers of these vinyl compounds, non-diffusible polymers having at least one water-soluble group and active methylene group in the repeating unit described in U.S. Pat. No. 3,904,413 Can be used in combination. In the silver halide color photographic light-sensitive material according to the present invention, each light-sensitive emulsion layer contains a coupler that couples with the oxide of an aromatic primary amine developing agent to form yellow, magenta, and cyan dyes during color development. It is normal to have it contained in
Such couplers include known photographic couplers such as open-chain β-ketomethylene compounds, pyrazolone compounds, indazolone compounds, pyrazolotriazole compounds, pyrazolinebenzimidazole compounds, phenolic compounds, and α-naphthol compounds. can be used. These couplers can be 2-equivalent, 4-equivalent and 6- to 8-equivalent couplers such as those described in Research Disclosure Nos. 20714 and 20919, but from the standpoint of speeding up bleaching rates only. For example, it is preferable to use a 2-equivalent coupler with a smaller amount of developed silver. However, for various reasons4
Of course, the effects of the present invention can be obtained even when an equivalent coupler or a 6- to 8-equivalent coupler is used. Furthermore, various photographic additives such as ultraviolet absorbers (e.g. benzophenone compounds and benzotriazole compounds), dye image stabilizers (e.g. phenolic compounds, bisphenol compounds, hydroxychroman compounds, bisspiroroman compounds, hydantoin compounds, dialkoxybenzene compounds, hydroxybenzoic acid ester compounds, etc.), color turbidity and stain inhibitors (e.g. hydroquinone derivatives, etc.) ) surfactants (e.g. fluorine surfactants, alkylnaphthalene sulfonates, alkylbenzene sulfonates, succinic acid esters, polyalkylene oxide compounds, etc.), water-soluble anti-irradiation dyes (e.g. azo compounds, styryl compounds), compounds, oxonol compounds, triphenylmethane compounds, anthraquinone compounds, etc.), hardening agents (e.g. halogen-substituted S-triazine compounds, activated vinyl compounds, ethyleneimino compounds, epoxy compounds, and water-soluble Aluminum salts, etc.), film property improvers (for example, glycerin, polyalkylene glycols, polymer aqueous dispersions (latex, etc.)) can be added to the support used in the silver halide color photographic light-sensitive material according to the present invention. Examples include paper, glass, cellulose, acetate, cellulose nitrate,
Supports such as polyesters, polyamides, and polystyrenes, or laminates of two or more substrates such as paper, polyolefin (e.g., polyethylene and polypropylene, etc.) and paper laminates, resin-coated paper, etc. depending on the purpose. It can be used as appropriate. Specific Effects of the Invention It has been well known that a 4,4'-diaminostilbene water-soluble fluorescent brightener is added to a color developing solution or a silver halide color photographic material. , increasing the whiteness of the white background of a photographic light-sensitive material for reflective printing;
As described in Research Disclosure No. 20733, silver halide color photographic materials containing benzoxazole green sensitizing dyes can be used as ultraviolet absorbers to absorb ultraviolet rays that are undesirable for photographic materials. It is not known to use 4,4'-diaminostilbene type water-soluble fluorescent brighteners for the purpose of accelerating the bleaching rate. As mentioned above, the present inventors have conducted extensive research to increase the bleaching speed in a dye image forming method in which bleaching and fixing are performed separately.
First, it was discovered that the aforementioned 4,4'-diaminostyreneben water-soluble fluorescent brightener has a desilvering promoting effect. Next, it was discovered that this desilvering promoting effect is only exhibited when the fluorescent whitening agent is present during color development processing. This is different from traditional desilvering accelerators, which were primarily added to the bleach or bleach-fix solution. Furthermore, the desilvering promoting action of the fluorescent brightener is effective when the desilvering process is carried out using a bleach-fixing solution, or even when the bleaching solution and fixing solution are used separately. When oxidizing agents other than carboxylic acid complex salts, such as red blood salts and dichromates, are used as oxidizing agents, no effect can be found. It was found that this effect was found only in the combination of a fluorescent brightener and an iron() polycarboxylic acid complex salt. The feature of the method for forming a dye image of the present invention is that the imagewise exposed silver halide photographic light-sensitive material is color-developed in the presence of a 4,4'-diaminostilbene-based water-soluble fluorescent whitening agent. The desilvering process is divided into a bleaching process and a fixing process, and the bleaching process is performed in the substantial absence of a fixing agent and in the presence of an iron() polycarboxylic acid complex salt with relatively weak oxidizing power as an oxidizing agent. By doing so, the bleaching speed and desilvering speed were increased. Specific Examples of the Invention Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these. Example 1 A silver halide photographic material having the following layer structure was prepared on polyethylene resin coated paper. Layer 1: Blue-sensitive silver chlorobromide emulsion (silver bromide 85 mol%) with an average grain size of about 0.65 μm, the following yellow coupler (Y-1) and a hydroquinone derivative (HQ
-1) A blue-sensitive silver halide emulsion layer (silver amount: 4.0 mg/100 cm ² , gelatin amount: 20 mg/100 cm ² ). Layer 2: first gelatin intermediate layer containing HQ-1 (gelatin amount 20 mg/100 cm ² ). Layer 3: Green-sensitive silver chlorobromide emulsion (silver bromide 90.5 mol%) with an average grain size of about 0.42 μm, green-sensitive halogen containing the following magenta coupler (M-1) and hydroquinone derivative (HQ-1) Silver emulsion layer (silver layer 3.8mg/100cm ² , gelatin amount 12mg/
^100cm2 ). Layer 4: HQ-1 and the following ultraviolet absorber
Two gelatin interlayers containing UV-1 and UV-2 (gelatin amount 18.5 mg/100 cm2 ⁾ . Layer 5: Red-sensitive silver chlorobromide emulsion (silver bromide 92.5 mol%) with an average grain size of about 0.35 μm, red-sensitive silver halide containing the following cyan couplers (C-1) and (HQ-1). Emulsion layer (silver content 2.8mg/100cm ² ,
Gelatin amount 15.5mg/ ^100cm2 ). Layer 6: Polyvinylpyrrolidone against gelatin
Gelatin protective layer containing 0.8% by weight (gelatin amount 10mg/100cm ² ). Each of the photosensitive silver halide emulsions described above was optically sensitized in a desired spectral region using the following optical sensitizer. blue sensitive emulsion green light-sensitive emulsion red light sensitive emulsion In addition, as samples related to the present invention, layers 2 and 4 in which water-soluble optical brighteners shown in Table 1 were added were also prepared. In addition, when adding the hydrophobic substances in each layer, sodium dodecylbenzenesulfonate was emulsified and dispersed in dioctyl phthalate as a high-boiling organic solvent in the presence of ethyl acetate as an activator. On the other hand, for the hardening of each gelatin film, 14.5 mg of bis(vinylsulfonylmethyl) ether was added per 1 g of gelatin in layers 1, 2, 3, and 6 as a hardening agent.
was added to harden the membrane. The obtained sample was heated at 45℃ and 80% relative temperature for 24 hours.
After storage for a time, the sample was exposed to blue, green, and red monochromatic light. (Exposure was carried out under conditions such that the reflection density was around 2.0 when developed under the following conditions.) A sample of this exposure agent was processed according to the following processing steps. Processing process Color development 33℃ 3 minutes 30 seconds Washing with water 30-34℃ 30 seconds Bleach 33℃ 0 seconds, 30 seconds, 45 seconds, 60 seconds, 75 seconds Washing with water 30-34℃ 30 seconds Fixing 20-30℃ Wash with water for 1 minute, dry for 2 minutes at 30-34℃, and process with color developer for 2 minutes at 70-80℃.

[Table] Bleach solution A formula to adjust to 700ml Ethylenediaminetetraacetic acid 12g Iron ethylenediaminetetraacetate () Ammonium 65g Sodium dithionite 2.5g 28% aqueous ammonia 15ml Ammonium bromide 80g 1 with pure water, 28% Adjust the pH to 6.0 with aqueous ammonia or sulfuric acid. Fixer formula Pure water 800ml Sodium thiosulfate 155g Sodium sulfite 12g Adjust to 1 with pure water. A certain area of the obtained sample was immersed in a 0.08N KCN solution to completely dissolve the remaining silver amount, and then measured with an atomic absorption photometer to determine the silver amount. The results are shown in Table 1. From the results in Table 1, samples 1 to 5 related to the present invention
Compared to sample 6 without fluorescent brightener,
It can be seen that a significant desilvering promoting effect is observed for each of blue, green, and red exposures.

【table】

[Table] Comparative Example 1 The experiment of Example 1 was carried out by changing the composition of the bleaching solution to the one shown below. Bleach solution B Pure water 800ml Ferric chloride monohydrate 100g Citric acid 20g Potassium bromide 50g Add to pure water and make 1. The residual silver amount of the obtained sample was determined by the method described in Example-1. The results are shown in Table 2. Second
From the results shown in the table, when ferric chloride other than the iron() polycarboxylic acid complex salt according to the present invention is used as an oxidizing agent in the bleaching solution, the silver halide color photographic material contains It can be seen that the desilvering promoting property of the present invention cannot be found even when the fluorescent brightener according to the above is used.

【table】

[Table] Comparative Example 2 The experiment described in Example 1 was conducted in the same manner as in Example 1, except that the following treatment steps were performed. Processing process Color development 33℃ 3 minutes 30 seconds Bleach-fix 33℃ 0 seconds, 36 seconds, 45 seconds, 60 seconds Washing 30-34℃ 3 minutes Dry 70-80℃ 2 minutes Bleach-fix solution

[Table] The residual silver content of the obtained samples was determined by the method described in Example 1, but no substantial significant difference was observed between those containing and those containing no optical brightener. Example 2 Sample 6 described in Example 1 (without fluorescent brightener)
The desilvering properties were evaluated according to the method described in Example 1. However, here, the bleaching solution and fixing solution described in Example 1 were used, and the fluorescent whitening agent listed in Table 3 was added to the color developing solution. The results of the desilvering test are shown in Table 3. From the results in Table 3, it can be seen that the effects of the present invention can be sufficiently exhibited even when a fluorescent whitening agent is added to the color developing solution.

【table】

[Table] Example 3 On a transparent cellulose triacetate film support, the following layers were sequentially provided from the support side,
A silver halide color photographic material was prepared. Layer 1: Antihalation layer containing black colloidal silver (silver content 3 mg/100 cm ² ) and gelatin 8 mg/100 cm ² . Layer 2: First intermediate layer containing 7 mg/100 cm ² of gelatin. Layer 3: Silver bromide emulsion (average grain size 0.6 μm) and silver bromide emulsion (average grain size 0.8 μm) were mixed at a ratio of 2:1 and after gold-sulfur root enhancement, silver halide 1 per mole 30mg, 120mg, and 20mg combined with color sensitized low sensitivity red sensitive silver bromide emulsion, cyan coupler C-2 Colored cyan coupler CC-1 DIR compound DI-1 A low-sensitivity post-photosensitive silver bromide emulsion layer containing (silver amount
18mg/100cm ² , gelatin 18mg/100cm ² ). Layer 4: Silver bromide emulsion (average grain size 1.3 μm) was sensitized with gold-sulfur to give RSD-2 per mole of silver halide.
High-sensitivity red-sensitive silver bromide emulsion color-sensitized with 100mg, RSD-3 50mg, RS2D-4 20mg, cyan coupler C-1, colored cyan coupler CC
-1 and the DIR compound DI-1 (silver content: 11 mg/100 cm ² , gelatin content: 13 mg/100 cm ² ). Layer 5: Same as layer 2 Layer 6: Silver bromide emulsion (average grain size 0.6 μm) and silver bromide emulsion (average grain size 0.3 μm) were mixed at a ratio of 2:1, and gold-sulfur sensitization was applied. After that, silver halide 1
Per mole, GSD-1 40mg, 30mg, and 20 mg of color-sensitized high-sensitivity green-sensitive silver bromide emulsion, magenta couplers M-2 and M-
3 M-2 M-3 Colored magenta coupler CM-1 Low-sensitivity green-sensitive silver bromide emulsion layer containing DIR compound (DI-1) (silver content 16 mg/100 cm ² , gelatin content 17 mg/100 cm ² ). Layer 7: Silver bromide emulsion (average grain size 1.2 μm) was gold-sulfur sensitized to give GSD-1 per mole of silver halide.
50mg, GSD-2 30mg, and GSD-3 70mg
Highly sensitive green-sensitive silver bromide emulsion, magenta coupler (M-1) and (M-
2) Colored magenta coupler (CM-1)
and a high-sensitivity green-sensitive silver bromide emulsion layer containing a DIR compound (DI-1) (silver amount 9 mg/100 cm ² ,
Gelatin amount 10mg/ ^100cm2 ). Layer 8: Same as layer 2. Layer 9: Yellow filter layer (silver amount 2 mg/100 cm ² , gelatin amount 14 mg/100 cm ² ) containing yellow colloidal silver, HQ-1 and polyvinylpyrrolidone (average molecular weight approximately 200,000). Layer 10: Silver bromide emulsion (average grain size 0.6 μm) gold-sulfur sensitized, containing 1 mole of silver halide 80mg, low-sensitivity blue-sensitive silver bromide emulsion sensitized to blue, yellow coupler Y-2 A low-sensitivity blue-sensitive silver bromide emulsion layer containing (silver amount
11mg/100cm ² , gelatin amount 18mg/100cm ² ). Layer 11: Silver bromide emulsion (average grain size 1.3 μm) was gold-sulfur sensitized, then BSD-2 was sensitized with silver halide 1
High-sensitivity blue-sensitive silver bromide emulsion layer containing yellow coupler Y-2 (silver amount 12 mg/mol).
100cm ² , gelatin amount 18mg/100cm ² ). Layer 12: Intermediate layer containing HQ-1 (gelatin amount 8
mg/ ^100cm2 ). Layer 13: Protective layer containing 10mg/ ^100cm2 of gelatin. In addition, the following hardening agent was added to layers 2, 5, 8, and 12 as a hardening agent. Desilvering property was evaluated using the obtained sample and the method described in Example 2. However, the treatment steps and treatment liquid prescription are as follows. Processing process Color development 38℃ 3 minutes 15 seconds Bleaching 38℃ 3 minutes 30 seconds 4 minutes 30 seconds 5 minutes 30 seconds Washing with water 30-35℃ 2 minutes 10 seconds Fixing 38℃ 6 minutes 30 seconds Washing with water Stable at 30-35℃ for 6 minutes and 30 seconds 38℃ for 2 minutes and 10 seconds [Color developer]

[Bleach solution]

Iron()ammonium ethylenediaminetetraacetate
100g Ammonium ethylenediaminetetraacetate 10g Ammonium bromide 150g Glacial acetic acid 10ml Add pure water to make 1, and adjust the pH to 6.0 using 28% aqueous ammonia. [Fixer] Ammonium thiosulfate 190g Sodium sulfite 10g Sodium metabisulfite 1.5g Add pure water to 1, and adjust to PH=6.0 using acetic acid and aqueous ammonia. [Stabilizing solution] Formalin (37% aqueous solution) 1.5 ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5 ml Add pure water to make 1. The amount of residual silver in the resulting sample was measured as described in Example 2. The results are shown in Table 4. The results shown in Table 4 show that the effects of the present invention can be obtained even when a pure silver bromide emulsion containing no silver chloride is used.

【table】

Claims (1)

[Claims] 1 A silver halide photographic light-sensitive material having a silver halide emulsion layer containing silver halide that does not contain silver iodide is subjected to imagewise exposure, and then color development treatment,
In a method of forming a dye image by carrying out bleaching treatment and fixing treatment in this order, the color development treatment is carried out in the presence of a 4,4'-diaminostilbene water-soluble optical brightener, and the bleaching treatment is 1. A method for forming a dye image, which is carried out in the presence of an iron() polycarboxylic acid complex salt and in the substantial absence of a fixing agent.