JPS5946385B2 - Color photo processing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic material (hereinafter referred to as a color photographic processing method) for developing, bleaching and fixing an exposed silver halide color photographic material. In particular, the present invention relates to an improved bleaching method that accelerates bleaching to shorten processing time and performs sufficient bleaching to form color photographic images of good quality.

Generally, the basic processing steps for silver halide color photographic materials are a color development step and a desilvering step.

That is, the exposed silver halide color photographic material is
In the color development step, silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former to provide a dye image. Color photographic materials then undergo a desilvering process, in which the silver produced in the previous process is oxidized by the action of an oxidizing agent (commonly known as a bleaching agent), and then a complex of silver ions, commonly known as a fixing agent, is removed. It is dissolved by the curing agent and removed from the photographic material. Therefore, only dye images are created in the photographic material. In addition to the two basic steps of color development and desilvering mentioned above, the actual development process includes auxiliary steps to maintain the photographic and physical quality of the image, or to improve the storage stability of the image. It is accompanied by For example, a hardening bath to prevent excessive softening of the photosensitive layer during processing, a stopping bath to effectively stop the development reaction,
Examples include an image stabilizing bath for stabilizing an image and a film removal bath for removing a packing layer from a support. In addition, the above-mentioned desilvering process may be carried out in one step using a bleach-fixing bath containing a bleaching agent and a fixing agent, or may be carried out in separate baths.
Sometimes it is done in two steps: a bleaching bath and a fixing bath.

Generally, oxidizing agents used in bleaching solutions include red blood salts, potassium dichromate, ferric ion complexes, and persulfates.

Among these, although the bleaching solution using red blood salt has an excellent bleaching effect, ferrician ion and its reduced form ferrician are discharged due to overflow during processing and carried into the washing water after bleaching. Ions undergo photochemical oxidation to produce cyanide. These cyanide compounds are highly toxic and cause great harm. Therefore, it is desired to develop a bleaching agent to replace red blood salt. Ferric ion complex salts are sometimes used as bleaching agents in bleach-fix solutions for color photographic paper.

(German Patent No. 866605, German Patent No. 96641
Specification No. 0, British Patent No. 746567, British Patent No. 9
(No. 33088, No. 1014396) However, since bleach-fixing agents containing ferric ion complex salts have weak oxidizing power, they have a high concentration of silver halide, and silver iodobromide is used. It is rarely used in color photosensitive materials for photography. Therefore, it is desirable to increase the oxidizing power of bleach and bleach-fix solutions using ferric ion complex salts. Further, the ferric ion complex salt can be used as a bleaching bath by containing bromide. However, the disadvantage of the ferric ion complex bleaching bath is that, like the bleach-fix solution, the bleaching blade is weak, so it takes a long time for bleaching. Second
Persulfates are known as bleaching agents other than iron ions and iron salts. Usually, persulfates are used as bleaching baths in combination with chloride. However, the disadvantage of persulfate bleach baths is that they are even weaker than ferric ion complexes and have significantly longer times to bleach. As mentioned above,
Bleaching solutions or bleach-fixing solutions using ferric ion complex salts or persulfates have weak bleaching blades, so they are rarely used for color films with photographic sensitivity that use a large amount of silver halide. It is, therefore, an object of the present invention to provide a photographic processing composition which has a bleach accelerating effect without adversely affecting the expressive properties. Another object of the present invention is to increase the bleaching edge of bleaching solutions or bleach-fixing solutions made of ferric ion complexes or persulfates.

Still another object of the present invention is a method for rapidly bleaching or bleach-fixing color photographic materials having photographic sensitivity.

For these purposes (1) In bleaching silver halide photosensitive materials with a bleaching solution or a bleach-fixing solution containing a ferric ion complex salt or a persulfate, a bath containing a compound represented by the following general formula (1) is used before bleaching. or use the following general formula (
This can be achieved by using a bleach solution or a bleach-fix solution containing the compound shown in 1).

More preferably (before bleaching, pretreatment is carried out in a bath containing a compound represented by the following general formula (1). General formula (1), where A is an optionally substituted amino group or a nitrogen-containing hetero group). Shows ring residues.

R1 (represents a hydrogen atom or carboxyl group. R2 represents a hydrogen atom or a methyl group. m represents 1 or 2, n represents O
Or represents 1. Z represents a hydrogen atom or a group represented by 8 (here, R represents an alkyl group having 1 to 3 carbon atoms, and may be substituted with a chlorine atom, a bromine atom, a carboxyl group, or an aminocarbonyl group).

XI (3 chlorine atoms or bromine atoms. A, Rl,
R2, m and n are as defined above). The substituent of the amino group represented by A is an alkyl group having 1 to 3 carbon atoms, and this alkyl group may be substituted with a hydroxy group, a methoxy group, or an ethoxy group. The amino group represented by A may be substituted with one or two alkyl groups. Further, the nitrogen-containing zero ring represented by A specifically means a saturated zero ring such as pyrrolidine, piperidine, piperazine, or morpholine, or an unsaturated zero ring such as imidazole, triazole, or indole. Z
is a group represented by [C7]x-, which is extremely advantageous in that it does not have the bad odor that is bothersome with -SH groups, the synthesis cost is low, and the effects of the invention are large.

Advantageous specific compound examples {J are as follows. As a method for synthesizing the compound represented by the general formula (1) of the present invention, there is, for example, a method as shown in the following formula. [However, A, Rl, R2
, m, and n have the same meanings as in general formula [1]] [A] or a nitrogen-containing heterocyclic amine, [B]
The amide base [C] can be obtained by condensing the acid chloride represented by in a solvent such as acetone, acetonitrile, or DMF in the presence of an organic base (e.g., pyridine, triethylamine, etc.) as a dehydrochlorination agent. .

In this condensation reaction, when [A] is a diamine consisting of a trisubstituted amine and a monosubstituted amine or a nitrogen-containing heterocyclic amine, only one type of amide [C] is produced, which is advantageous in terms of synthesis. When the chloride of CC] is reacted with thiourea in an alcohol, the isothiourea compound [D] can be easily obtained. CD] is one of the compounds included in the general formula [1], and a compound in which Z is a hydrogen atom can be easily synthesized from [D] by hydrolysis in the presence of an alkali or acid. This product was treated with R-C-Cl or R in the presence of a dehydrohalogenating agent.
By reacting with O-C-Cl, a compound in which Z is -C-R or -C-0-R can be obtained.

Furthermore, a disulfide type compound can be obtained by treating a compound in which Z is a hydrogen atom with hydrogen peroxide. The compound represented by the general formula (1) of the present invention is contained in a so-called pre-treatment liquid, which is used in a step before a treatment step using a bleach solution or a bleach-fix solution.

In this case, the pretreatment solution refers to the processing solution after the development step, and refers to the processing solution before the bleach solution (or bleach-fix solution). It is used immediately before the processing step with a bleach-fix solution, but it does not necessarily have to be immediately before, and another processing solution may be interposed between the pre-processing solution and the bleach solution or bleach-fix solution. When immediately followed by a bleaching or bleach-fixing step, the desired bleach-accelerating effect cannot be obtained even if the compound of the present invention is included only in the developer solution. It may be contained only in the processing solution, or it may be contained in both the bleaching solution or bleach-fixing solution and the pretreatment solution.That is, a desired bleaching accelerating effect can be obtained in any of these addition modes. The amount of the compound of the present invention to be added to these solutions varies depending on the type of processing solution, the type of photographic material to be processed, the processing temperature, the time required for the intended processing, etc. A suitable amount is 10-3 to 2×10-1 mol/l, preferably 1×10-2 to 4×10-2 mol/l.However, in general, when the amount added is small, the bleaching accelerating effect is small; If the amount is larger than necessary, precipitation may occur and contaminate the photographic materials being processed, so it is preferable to determine the optimum range for the amount added depending on each individual case.The present invention When adding a compound to a processing solution, it is common to dissolve it in water, alkali, organic acid, etc. beforehand, but if necessary, it can be dissolved and added using an organic solvent. However, it has no effect on its bleaching promotion effect.

When the compound of the present invention is contained in a prebath of a bleach or bleach-fix solution, a variety of compositions can be used as the prebath.

The prebath with the simplest composition is an aqueous solution in which the compound of the present invention is simply dissolved, but it may also contain acids such as acetic acid or boric acid, alkalis such as sodium hydroxide, or sodium sulfite, sodium acetate, sodium thiosulfate, or sodium borate. Aqueous solutions suitably containing salts such as sodium carbonate, sodium bicarbonate, etc. can also be advantageously used as pre-baths. Any pH value can be used for the pre-bath, and the effects of the present invention can be effectively achieved with any pH value, but if the pH value is too high, stains may occur, so in general, P
It is preferable to use it at H9 or lower. In the pre-bath, if necessary, anti-settling agents made of various chelate compounds, hardeners made of various compounds such as alum and aldehyde, 6PH buffering agents, fixing agents of halogen salts, and sulfurous acid are added. Antioxidants such as salts, hydroxylamine and hydrazine, anti-swelling agents such as sodium sulfate and magnesium sulfate6
A surfactant or the like can be contained. For example, a washing treatment, a stop treatment, a stop fix treatment, etc. can be interposed between the prebath and the bleach bath or bleach-fix bath. When the compound is added, a similar bleaching accelerating effect can be obtained.However, when the compound of the present invention is contained only in the prebath, it may be added to the prebath (or in the step immediately before the bleach bath or bleach-fix bath). The ferric ion complexes that can be used in the bleach solution or bleach-fix solution constituting the present invention include ferric ion and 5-aminopolycarboxylic acid, aminopolyphosphonic acid, or salts thereof. It is a complex with a chelating agent.

Aminopolycarboxylic acid salts or aminopolyphosphonic acid salts are salts of aminopolycarboxylic acids or aminopolyphosphonic acids with alkali metals, ammonium, or water-soluble amines. Alkali metals include sodium, kaliwam,
Water-soluble amines include alkylamines such as methylamine, diethylamine, triethylamine, and butylamine, ring amines such as cyclohexylamine, arylamines such as aniline and m-toluidine, and multiple amines such as pyridine, morpholine, and piperidine. It is an elementary amine. Typical examples of chelating agents such as aminopolycarboxylic acids and aminopolyphosphonic acids or salts thereof include ethylenediaminetetraacetic acid ethylenediaminetetraacetic acid dinatriwam salt ethylenediaminetetraacetic acid diammonium salt ethylenediaminetetraacetic acid tetra(trimethylammonium) salt ethylenediaminetetraacetic acid Tetrakaliwam acetate salt Ethylenediaminetetranatriwam salt Ethylenediaminetetraacetate trinatriwam salt DiethylenetriaminepentaacetateDiethylenetriaminepentanacetic acid pentasodium salt Ethylenediamine-(β-oxyethino(c)-1N,N)
',N'monotriacetic acid) ethylenediamine-N-(β-oxyethyno(c)-1N,N',N) trisodium acetate salt ethylenediamine-N-(β-oxyethyno(c)-1N,N', N' Triammonium monotriacetate Propylene diamine Tetra acetate Propylene diamine Tetra acetate dinatriwam salt Nitrilotriacetic acid Nitrilotriacetic acid trinatriwam salt Cyclohexane diamine Tetra acetic acid Cyclohexane diamine Tetra acetic acid dina triwa salt Iminodiacetate dihydroxyethylglycine ethyl ether diamine Tetra acetic acid glycol ether diamine Tetra acetic acid ethylene diamine Phenylene diamine tetrapropionate 1,3-diamine propanol tetraacetate -N,N,N',N'-
Tetramethylenephosphonic acid ethylenediamine-N,N,
Examples include N',N'-tetramethylenephosphonic acid, 1,3-propylenediamine-N,N,N',N'-tetramethylenephosphonic acid, but are not limited to these exemplified compounds.

The ferric ion complex salt may be used in the form of a complex salt, or as a ferric ion complex salt.
In a solution using an iron salt, such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium nitrate, ferric phosphate, etc., and a chelating agent, such as aminopolycarboxylic acid or aminopolyphosphonic acid. A ferric ion complex salt may be formed.

When used in the form of a complex salt, one type of complex salt or two or more types of complex salts may be used. On the other hand, the second
When forming a complex salt in a solution using an iron salt and a chelating agent, one type or two or more types of ferric salts may be used. Furthermore, one type (or two or more types) of chelating agents may be used. Also, in any case, the chelating agent may be used in excess of the amount required to form the ferric ion complex. A bleaching solution containing an iron ion complex (3) or a bleach-fixing solution may contain hydrogen peroxide.

The persulfate used in the bleach solution or bleach-fix solution constituting the present invention is an alkali metal persulfate such as potassium persulfate or sodium persulfate, or ammonium persulfate. In addition to the ferric ion complex salt and the above compounds, the bleaching solution constituting the present invention may contain bromides such as potassium bromide, sodium bromide, ammonium bromide, or chlorides such as potassium bromide, sodium chloride, ammonium chloride, etc. can be included.

In addition, one or more inorganic acids having a PH buffering capacity such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. , organic acids and their salts can be added. in this case,
The amount of ferric ion complex salt per 11 parts of bleaching solution (0.1 to 2
molar, and the pH of the bleaching solution is 3.0 to 8.01, particularly 4.0 to 7.0, in the case of ferric ion complex salt when used.
It is desirable that the value is 1.0 to 7.0 in the case of persulfuric acid.
In particular, it is desirable that the value be 2.0 to 6.0.

On the other hand, when the composition of the present invention is used as a bleach-fixing agent, a conventional fixing agent may be used, i.e. thiosulfates such as sodium thiosulfate, ammonium thiosulfate, ammonium thiosulfate, potassium thiosulfate: thiocyanic acid. A water-soluble silver halide solubilizing agent such as a thiocyanate salt such as natriwam, ammonium thiocyanate, or potassium thiocyanate; a thioether compound such as ethylene histhioglycolic acid or 3,6-dithia-1,8-octanediol; These can be used alone or in combination of two or more.

The amounts of each component in the bleach-fix composition are as follows:
The amount of the ferric ion complex salt is 0.1 to 2 mol, and the amount of the fixing agent is 0.2 to 4 mol.

The bleach-fixing agent can contain the aforementioned additives and sulfites that can be added to the bleach solution, such as sodium sulfite, potassium sulfite, ammonium sulfite, and the like.

Furthermore, compounds already known to have bleach-fix accelerating properties, such as polyamine compounds described in Japanese Patent Publication No. 45-8836, thiourea derivatives described in Japanese Patent Publication No. 45-8506,
Iodides described in German Patent No. 1127715, polyethylene oxides described in German Patent No. 966410, nitrogen-containing heterocyclic compounds described in German Patent No. 1290812, other thioureas, etc.
It is also possible to contain more than one type. In addition, the bleach-fix solution P
H (when used, it is usually 4.0 to 8.0, particularly preferably 5.0 to 7.0. The above bleach or bleach composition can be used as a bleaching solution or replenisher liquid and
It refers to both bleach-fixer formulations for preparing bleach solutions as working solutions or replenishment solutions.

In the case of a preparation of two or more liquids, the pH of the liquid containing the ferric ion complex can be further increased regardless of the above pH range. The object of the present invention can also be achieved by adding the compound represented by the general formula (1) to the bleaching solution or bleach-fixing solution, but in this case, the amount added is 1 x 10-3 mol/ l~2×10−1 mol/! Preferably 1×10−2
mol/l to 4 x 10-2 mol/l for bleach-fix solution 1 x 1
0-3 mol/l to 2 x 10-1 mol/13 preferably l
x10-2 mol/l to 4 x 10-2 mol/l. The first aromatic amino color developer used in the color developer in the present invention includes known ones that are widely used in various color photographic processes.

These developers include aminophenol and p-phenylenediamine derivatives. These compounds (1
Since it is more stable than the free state, it is generally used in the form of a salt, such as a hydrochloride or a sulfate. In addition, these compounds generally have a concentration of about 0.19 to about 309 for color developer 12.
more preferably about 1 for color developer 1'.
It is used at a concentration of 9 to about 159. As an aminophenol developer (for example, 0 aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2
-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

A particularly useful primary aromatic amino color developer is an N,N-dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, particularly useful examples include N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, -amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β- Hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N(2-methoxyethino(c)-N-
Examples include ethyl-3-methylaniline-p-toluenesulfonate. In addition to the first aromatic amino color developer, the alkaline color developer used in the present invention further contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate, and carbonate. It can also optionally contain alkaline agents such as kaliwam, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickening agents, and the like.

The pH value of this color developer is usually 7 or higher, most commonly about 10 to about 13. According to the present invention, the silver halide color photographic material processed in the presence of the compound of the present invention is a known color photographic material, preferably a variety of negative-working color photographic materials containing couplers or (It can be used particularly advantageously when processing color print photographic materials, or when processing color photographic materials made for reversal color processing, and furthermore, color X-ray photographic materials, single color photographic materials, etc.). Layer-specific color photographic materials can also be processed.Alternatively, there is no problem in processing the coupler in the developer.Silver halide photographic materials that can be applied to the present invention are those in which the color former is Internal development methods included in photosensitive materials (for example, U.S. Pat. No. 2,376,679, U.S. Pat. No. 2,801)
In addition to external development methods in which a coloring agent is contained in the developer (for example, U.S. Pat. No. 2252),
No. 718, No. 2592243, No. 2590970
(described in the specification etc.).

Further, as the coloring agent, any coloring agent generally known in the art can be used. For example, cyan color formers are based on a naphthol or phenol structure and form indoaniline dyes by coupling, magenta color formers have a 5-pyrazolone ring with an active methylene group as a backbone structure, and yellow color formers have are those with a benzoylacetanilide, pivalylacetanilide, or acylacetanilide structure that has an active methylene chain, and those that have a substituent at the coupling position.
You can use any of them even if you don't have one. As described above, both so-called 2-equivalent couplers and 4-equivalent couplers can be used as color formers. As the silver halide emulsion that can be used, any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used. It may be something. Furthermore, as protective colloids for these silver halides, natural products such as gelatin, as well as various products obtained by synthesis can be used. The silver halide emulsion may contain conventional photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants. Example 1 Using polyethylene terephthalate with an undercoat layer as a support, the following emulsions were sequentially applied.

First layer (red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 5 mol %) containing 109 silver halide and 59 gelatin per emulsion 1009
In contrast, gelatin solution 5009 in which cyan coupler (C-1) was emulsified and dispersed (molar ratio of silver and coupler was 7:1),
50cc of 1% aqueous solution of stabilizer (A-1), coating agent (T-
1) 1(!) 50CC of aqueous solution, including hardening agent (H-1)
20! ) An emulsion solution to which 20 cc of an aqueous solution was added was applied so that the dry film thickness was 4 μm.

Second layer (intermediate layer) Color mixing prevention agent (A
gelatin aqueous solution 1009 emulsifying and dispersing gelatin-2), coating agent (T-1) 1 (F6 aqueous solution 50 cc and film tilting agent (H-
1) 201) A gelatin solution to which 20 cc of aqueous solution was added was applied so that the dry film thickness was lμ.

Third layer (green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 5 mole 01) containing 109 silver halide and 59 gelatin per emulsion 1009
09, gelatin solution 7009 in which magenta coupler (C-2) was emulsified and dispersed (the molar ratio of silver and coupler was 7:1)
), 1(:Ff) aqueous solution of stabilizer (A-1) 50CC,
50 cc of 1% aqueous solution of coating agent (T-1) and hardener (H
An emulsion solution containing 20 cc of a 2% aqueous solution of -1) was applied to give a dry film thickness of 4 μm.

Fourth layer (yellow filter layer) 5% gelatin aqueous solution with colloidal silver dispersed 10009
To this, 100 cc of a 1% aqueous solution of the coating agent (T-1) and 20 cc of a 2% aqueous solution of the hardener (H-1) were added so that the amount of coated silver was 0.5η/100 (177f). did.

Fifth layer (blue-sensitive emulsion layer) Silver iodobromide emulsion containing 109 silver halide and 59 gelatin per emulsion (silver iodide 5 mol 01)) 100
0f), gelatin solution 5009 in which yellow coupler (C3) was emulsified and dispersed (molar ratio of silver and coupler {is 7
:1), 50 cc of 1% aqueous solution of stabilizer (A-1), 50 cc of 1% aqueous solution of coating agent (T-1), and hardener (H-1)
) to which 20cc of a 2% aqueous solution was added to make an emulsion with a dry film thickness of 4
It was applied so that it was μ.

Sixth layer (protective layer) 1% aqueous solution of coating agent (T-1) in 5% gelatin aqueous solution
1 (:!) aqueous solution of 00CC hardener (H-1) 20CC
A gelatin solution to which was added was applied so that the dry film thickness was 1 μm.

← [Emulsification method: Cyan coupler (C-1) 759 was dissolved in a mixture of 100 cc of dibutyl phthalate and 200 cc of ethyl acetate, and this was dissolved in a 10% gelatin aqueous solution 6009.
emulsify it with a dispersion aid.

] [Emulsification method: Dissolve magenta coupler (C-2) 759 instead of cyan coupler (C-1)? and emulsify in the same manner as in the case of cyan coupler (C-1).

] [Emulsification method Emulsification is carried out in the same manner as in the case of cyan coupler (C-1) except that yellow coupler (C-3) 909 is dissolved instead of cyan coupler (C-1).

] Emulsification formula Color mixing inhibitor (A-2) 1009 dibutyl phthalate 2
00CC and 200CC of ethyl acetate, and emulsified in a 10% aqueous gelatin solution 5009 with a dispersion aid.

The color reversal film obtained in this way was given appropriate exposure, and according to the following development process, the general formula (
Development processing was carried out using various types of pre-baths to which the compounds shown in 1) were added.

For each film sample subjected to the above-described development process, the amount of silver remaining in the sample was measured by X-ray fluorescence analysis.

The results are as follows. Films treated with such a pre-bath containing the compound of the present invention were desilvered to such an extent that the remaining undesilvered silver was practically no problem, and a clear color image was obtained. The compounds of the present invention have enabled rapid development processing with low pollution.

Example 2 Even when the bleaching solution in Example 1 was replaced with a bleaching solution having the following composition and the film was developed, the film treated with the pre-bath containing the compound of the present invention was the same as the pre-bath not containing the compound of the present invention. Much clearer and sharper color images were obtained than with bath-processed films.

Example 3 A color negative film sample was prepared by sequentially applying the following layers 1 to 11 on a subbed cellulose triacetate film starting from the first layer.

1st layer (antihalation layer) Gelatin layer containing black colloidal silver 2nd layer (intermediate layer) Gelatin layer containing an emulsion of 2,5-di-t-octylhydroquinone 3rd layer (low sensitivity red-sensitive emulsion layer) Low-sensitivity silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.8μ, gelatin 709/Kg emulsion) 4th layer (high-sensitivity red-sensitive emulsion layer) High-sensitivity silver iodobromide emulsion (silver iodide 5 mol%,
Average particle size 1.2μ, gelatin 709/Kg emulsion)
5th layer (intermediate layer) 6th layer (low-sensitivity green-sensitive emulsion layer) same as 2nd layer Low-sensitivity silver iodobromide emulsion (silver iodide 7 mol%, average grain size 0.8μ, gelatin 709/Kg emulsion) ) 7th layer (high-sensitivity green-sensitive emulsion layer) High-sensitivity silver iodobromide emulsion (silver iodide 8 mol%,
Average particle size 1.2μ, gelatin 709/Kg emulsion)
8th layer (yellow filter layer) yellow colloidal silver and 2,5-
Gelatin layer 9th layer (low-sensitivity blue-sensitive emulsion layer) containing an emulsified dispersion of di-t-octylhydroquinone Low-sensitivity silver iodobromide emulsion (silver iodide 7 mol%, average grain size 0.8μ, gelatin 709/ Kg emulsion 10th layer (high sensitivity blue sensitive emulsion layer)
High-sensitivity silver iodobromide emulsion (silver iodide 8 mol %, average grain size 1.3 μm, gelatin 709/K9 emulsion) Each layer contains a gelatin hardener, a coating aid, etc. in addition to the above composition.

Materials used: Sensitizing dye 1: Anhydro-5, Dichloro-3,3'
-Disulfopropyl-9-ethylthiacarbocyanine hydroxide pyridinium salt; Anhtrow 9
-ethyl-3,3'-di-(3-sulfopropyl)-4
, 5,4',5' dibenzothiacarphocyanine hydroxide triethylamine salt sensitizing dye I; 5,5,5',6'-tetrachloro-1,1'
-diethyl 3,3'-di(sulfopropoxyethoxyethyl)-imidazolocarbocyanine hydroxide sodium salt coupler A; l-hydroxy-N-[γ-(
2,4-di-t-amylphenoxypropino(c)]2
- Naphthamide coupler B: 1-hydroxy-4-{2
-(2hexyldecyloxycarbonyl)phenylazo}-2-{N-(1-naphthal)}-naphthamide coupler C; 1-(2,4,6-trichlorophenyl)-3
-{3-[α-(2,4-di-t-amylphenoxy)
Acetamide]benzamide-5-pyrazolone coupler D: l-(2,4,6-trichlorophenyl)-3-[
3-{α-2,4-di-t-amylphenoxy)acetamide}benzamide]-14-methoxyphenylazo-5-pyrazolone coupler E: α-(2,4-dioxo-5,5′ dimethyloxazolidini) )-α-pivaloyl 2-chloro-5-{αL(2,4-di-t-amylphenoxy)butyramide}acetanilide coupler F: α-
{5(6)-(3-methyl-2-benzothiazolylideneamino)-1-benzotriazolyl}-α-(4-octadecyloxybenzoino(ha)-2-ethoxyacetoacetanilide above) Each coupler emulsion was prepared by dissolving the coupler in a mixture of dibutyl phthalate and tricresyl phosphate, and dispersing the coupler in O/W form in a gelatin solution using sorbitan monolawalate, road oil, and sodium dodecylbenzenesulfonate as dispersing emulsifiers. It is dispersed.

Exposure to this photographic element (1/50 second, 10 C.M.S.)
After giving the film, development processing was carried out at 38° C. according to the following processing steps.

V7s'N=1VゞV The composition of the treatment liquid used in each step was as follows.

Color development'J~-'JH'Ir. v The above development process was carried out using a prebath having the same composition as above except that compound (3) was not added.

By using the compounds of the invention in the prebath, bleaching was achieved in a significantly shorter time. Preferred embodiments of the present invention are as follows.

1. Embodiments in which persulfates are used as bleaching agents in the claims.

2. An embodiment in which a complex of an organic acid and ferric ion is used as a bleaching agent in the claims.

3. An embodiment in which a ferric complex salt of ethylenediaminetetraacetic acid is used as the bleaching agent in the claims.

4. An embodiment in which a pretreatment is performed in a prebath, stop bath, or fixing bath containing a compound represented by the general formula (1) in the claims.

5. An embodiment in which the prebath is placed immediately before the bleaching bath or bleach-fixing bath in 4 above.

Claims (1)

[Claims] 1. Before bleaching, pretreatment is performed in a bath containing a compound represented by the general formula (I), or a bleaching solution or a bleach-fixing solution containing the compound represented by the general formula (I) is used. and a bleaching method for a silver halide color light-sensitive material, characterized in that the bleaching agent is a ferric ion complex salt or a persulfate salt. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [However, A indicates an amino group or a nitrogen-containing heterocyclic residue that may be substituted. R^1 represents a hydrogen atom or a carboxyl group. R^
2 represents a hydrogen atom or a methyl group. m is 1 or 2, n
represents 0 or 1. Z represents a hydrogen atom or a group represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. R represents an optionally substituted alkal group, and X represents a halogen atom. ]