JPS6116066B2 - - 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) in which an exposed silver halide color photographic material is developed, bleached, and fixed. The present invention relates to an improved bleaching method capable of shortening processing time and performing 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, in the color development step of the exposed silver halide color photographic material, the silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with the coloring agent to form a dye image. give. Afterwards, the color photographic material goes through 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 complexed with silver ions, commonly known as a fixing agent. It is dissolved by the 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. is accompanied by For example, a hardening bath to prevent excessive softening of the photosensitive layer during processing, a stop bath to effectively stop the development reaction, an image stabilizing bath to stabilize the image, or a film removal bath to remove the packing layer of the support. Examples include bathing. Further, the above-mentioned desilvering step may be carried out in one step using a bleach-fixing bath in which a bleaching agent and a fixing agent coexist, or may be carried out in two steps, a bleaching bath and a fixing bath, using separate baths. Generally, oxidizing agents used in bleaching solutions include red blood salts, potassium dichromate, ferric ion complexes, and persulfates. Although the bleaching solution using red blood salt has an excellent bleaching effect, ferrician ions and its reduced form ferrician ions are discharged due to overflow during processing and carried into the washing water after bleaching. undergoes 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. 966410, British Patent No. 746567, German Patent No. 933088,
(Specification No. 1014396) However, since bleach-fixing agents containing ferric ion complex salts have weak oxidizing power, color photosensitive materials for photography that have a high concentration of silver halide and use silver iodobromide is hardly used. 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 drawback of the ferric ion complex bleaching bath is that, like the bleach-fix solution, its bleaching power is weak, so it takes a long time for bleaching. Persulfates are known as bleaching agents other than ferric ion complex salts. Typically, persulfates are used as bleach baths in the presence of chloride. However, the disadvantage of persulfate bleach baths is that
It has even weaker bleaching power than ferric ion complex salts and takes a significantly longer time to bleach. As mentioned above, bleaching solutions or bleach-fixing solutions using ferric ion complex salts or persulfates have weak bleaching power, so they are rarely used for color films with photographic sensitivity that use large amounts of silver halide. It has not been. It is therefore an object of the present invention to provide a photographic processing composition which has a bleaching accelerating effect without adversely affecting photographic properties. Another object of the present invention is to increase the bleaching power of bleaching solutions or bleach-fixing solutions comprising 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. These purposes are to bleach a silver halide photosensitive material using a bleaching solution or a bleach-fixing solution containing a ferric ion complex salt or a persulfate. or the following general formula (a).
Or, it can be achieved by using a bleach solution or a bleach-fix solution containing the compound shown in (b). More preferably, before bleaching, pretreatment is performed in a bath containing a compound represented by the following general formula (a) or (b). However, A represents an optionally substituted amino group or nitrogen-containing heterocyclic residue. R ¹ represents a hydrogen atom or a carboxyl group. R ² is a monovalent metal atom,
ammonium group, optionally substituted alkyl group, or

【formula】 or

Indicates a group represented by [Formula]. R ³ and R ⁴ are each a hydrogen atom, a hydroxyl group, an alkoxy group (e.g. methoxy group or ethoxy group), a halogen atom, a carboxyl group, -SO ₂ H
represents an alkyl group which may be substituted with a group, a -SO ₃ H group, or a group represented by A above. m is 1
or 2, and n represents an integer of 1 to 4. The substituent of the amino group represented by A has 1 to 3 carbon atoms.
is an alkyl group which may be substituted with a hydroxy group, a methoxy group or an ethoxy group. The amino group represented by A is one or two
may be substituted with an alkyl group. Further, the nitrogen-containing heterocycle represented by A specifically means a saturated heterocycle such as pyrrolidine, piperidine, piperazine or morpholine, or an unsaturated heterocycle such as imidazole, triazole or indole.
These heterocycles may be substituted with an alkyl group having 1 to 3 carbon atoms which may be substituted with a hydroxyl group, methoxy group or ethoxy group. Examples of alkyl groups for R ² , R ³ and R ⁴ include methyl, ethyl and propyl groups.
Examples of substituted alkyl groups for R ² , R ³ , and R ⁴ are −
_CH2Cl , _{-CH2CH2OH , -CH2CH2OCH3 , -
CH2CH2OC2H5 , _ _}

[Formula] −CH ₂ COOH, − CH ₂ CH ₂ COOH, −CH ₂ CH ₂ CH ₂ COOH, −
CH ² SO ₃ H, −CH ² CH ² SO ₃ H, −
CH ₂ CH ₂ CH ₂ SO ₃ H, - (CH ₂ ) ₄ SO ₃ H, -
_Mention may _be made _{of CH2SO2H} , _-CH2CH2SO2H , _- ( _{CH2 ) 3SO3H} or -( _CH2 ) _4SO2H . Furthermore, this substituted alkyl group is -CH ₂ CH ₂ -A, -(CH ₂ ) ₃ -
A, It may be. Examples of advantageous compounds are as follows. Examples of methods for synthesizing the compound of the present invention include the following method. [However, A, R ¹ , R ² , R ³ , R ⁴ , m, and n have the same meanings as in general formulas [a] and [b]. ] The compound of general formula [a] is a dithiocarbamic acid [B] obtained by reacting the amino form [A] with a solution of alcohol or acetone, etc., and carbon disulfide.
can be easily obtained by reaction with active chloride R ² Cl in the presence of, for example, an organic base (eg pyridine, triethylamine, etc.) as a dehydrohalogenating agent. Further, the compound of general formula [b] is dithiocarbamic acid [D] obtained by the reaction of amine [C] and carbon disulfide.
is easily synthesized by condensing with aminoalkyl chloride or nitrogen-containing heterocyclic alkyl chloride A-(CH ₂ )nCl in the presence of the above dehydrohalogenating agent. In the condensation reaction that produces [a] and [b], if the molecule itself has an amino group (especially a tertiary amino group), it acts as a dehydrohalogenating agent, so adding an organic base is necessary. It is not necessary. The compound represented by the general formula [a] or [b] of the present invention is contained in a so-called pre-treatment solution, which is used in a step before a treatment step using a bleach solution or a bleach-fix solution. In this case, the pretreatment liquid refers to a treatment liquid after a developing step, and before a bleaching solution or a bleach-fixing solution.
The pretreatment solution is usually used immediately before the bleach or bleach-fix solution, but it does not necessarily have to be immediately before, and other processing solutions may be used between the pretreatment solution and the bleach or bleach-fix solution. May intervene. When a bleaching or bleach-fixing step is performed immediately following the developing step, the desired bleaching accelerating effect cannot be obtained even if the compound of the present invention is contained only in the developer. The compound of the present invention may be contained only in the bleach solution or bleach-fix solution or a pretreatment solution thereof, or may be contained in both the bleach solution or bleach-fix solution and the pretreatment solution. That is,
Desired bleaching accelerating effects 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.
x10 ^-3 to 2 x 10 ^-1 mol/, preferably 1 x 10 ^-2 to 4 x 10 ^-2 mol/. However, in general, when the amount added is small, the effect of promoting bleaching is small, and when the amount added is larger than necessary, precipitation may occur and contaminate the photographic materials being processed. It is preferable to determine the optimal range as appropriate depending on the case. When adding the compound of the present invention to a treatment liquid, it is generally dissolved in water, an alkali, an organic acid, etc. beforehand, but if necessary, it is dissolved in an organic solvent before being added. However, it has no effect on its bleaching promotion effect. When the compound of the present invention is contained in a pre-bath of a bleach or bleach-fix solution, various compositions can be used as the pre-bath. 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. An aqueous solution suitably containing salts such as , sodium carbonate and sodium bicarbonate can also be advantageously used as a pre-bath. Any PH can be used for the pre-bath, and the effects of the present invention can be obtained advantageously in any case, but if the PH is too high, stains may occur, so in general, the PH is 9 or lower. It is preferable to use it in In the pre-bath, if necessary, anti-settling agents made of various chelate compounds, hardening agents made of various compounds including alum and aldehyde, PH buffering agents, fixing agents of halogen salts, Antioxidants such as sulfites, hydroxylamine and hydrazine, anti-swelling agents such as sodium sulfate and magnesium sulfate, surfactants and the like can be contained. For example, a water washing treatment, a stop treatment, a stop fix treatment, etc. can be interposed between the prebath and the bleach bath or bleach-fix solution, but even in such cases, the compound of the present invention may be added to the prebath. When this is done, a similar bleaching promoting effect can be obtained. However, when the compound of the present invention is contained only in the prebath, it is more desirable that the prebath be used in the step immediately before the bleach bath or bleach-fix bath. The ferric ion complex that can be used in the bleaching solution or bleach-fixing solution constituting the present invention is a complex of ferric ion and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or a salt thereof. Aminopolycarboxylic acid salts or aminopolyphosphonic acid salts are salts of aminopolycarboxylic acids or aminopolyphosphonic acids with alkali metals, ammonium, or water-soluble amino acids. Examples of alkali metals include sodium, potassium, lithium, etc.; examples of water-soluble amines include alkyl amines such as methylamine, diethylamine, triethylamine, and butylamine; ring amines such as cyclohexylamine; aryl amines such as aniline and m-toluidine; Heterocyclic amines such as pyridine, morpholine, and piperidine. Typical examples of chelating agents such as these aminopolycarboxylic acids and aminopolyphosphonic acids or their salts include: ethylenediaminetetraacetic acid ethylenediaminetetraacetic acid disodium salt ethylenediaminetetraacetic acid diammonium salt ethylenediaminetetraacetic acid tetra(trimethylammonium) salt ethylenediamine Tetraacetic acid tetrapotassium salt Ethylenediaminetetraacetic acid tetrasodium salt Ethylenediaminetetraacetic acid trisodium salt Diethylenetriaminepentaacetic acid Diethylenetriaminepentaacetic acid pentasodium salt Ethylenediamine-N-(β-oxyethyl)-
N,N',N'-ethylenediamine triacetate-N-(β-oxyethyl)-
N,N',N'-Triacetic acid trisodium salt ethylenediamine-N-(β-oxyethyl)-
N,N',N'-Triammonium triacetate Propylene diamine Tetra acetic acid Propylene diamine Tetra acetic acid disodium salt Nitrilotriacetic acid Nitrilotriacetic acid trisodium salt Cyclohexane diamine Tetra acetic acid Cyclohexane diamine Tetra acetic acid disodium salt Iminodiacetic acid dihydroxyethylglycine ethyl ether diamine Tetraacetic acid glycol ether diamine Tetraacetic acid ethylenediamine Tetrapropionic acid phenylenediamine Tetraacetic acid 1,3-diaminopropanol-N,N,N',
N'-tetramethylenephosphonic acid ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid 1,3-propylenediamine-N,N,N',
Examples include N'-tetramethylenephosphonic acid, but the compound is not limited to these exemplified compounds. Ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride,
Ferric nitrate, ferric ammonium sulfate, ferric phosphate
A secondary compound is produced in a solution using iron, etc. and a chelating agent such as aminopolycarboxylic acid or aminopolyphosphonic acid.
An iron ion complex salt may be formed. When used in the form of a complex salt, one type of complex salt may be used,
Also, 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. In any case, the chelating agent may be used in excess of the amount required to form the ferric ion complex. Further, the bleaching solution or bleach-fixing solution containing the above-mentioned ferric ion complex salt 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-mentioned compounds, the bleaching solution constituting the present invention contains bromides such as potassium bromide, sodium bromide, ammonium bromide, or chlorides such as potassium chloride, sodium chloride, ammonium chloride, etc. can be included. other,
One or more inorganic acids with 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, organic Acids and their salts can be added. In this case, the amount of ferric ion complex salt per bleaching solution is 0.1 to 2 mol, and the pH of the bleaching solution is 3.0 to 8.0 when using ferric ion complex salt.
In particular, it is desirable that it be 4.0 to 7.0, and in the case of persulfates, it is desirable that it be 1.0 to 7.0, especially 2.0 to 6.0. On the other hand, when the composition of the present invention is used as a bleach-fix solution, conventional fixing agents, i.e. thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate: sodium thiocyanate, thiocyanic acid Thiocyanates such as ammonium, potassium thiocyanate: ethylene thioglycolic acid, 3,6
It is a water-soluble silver halide solubilizing agent such as a thioether compound such as -dithia-1,8-octanediol, and these can be used alone or in combination of two or more. The amounts of each component in the bleach-fix composition are 0.1 to 2 mol for the ferric ion complex salt, 0.2 to 4 mol for the fixing agent, and 0.2 to 4 mol for the ferric ion complex per bleach-fix solution. Additives such as those mentioned above and sulfites such as sodium sulfite, potassium sulfite, ammonium sulfite, etc. can be included. Furthermore, compounds already known to have bleach-fix accelerating properties, such as
Polyamine compound described in Publication No. 45-8836, published by Tokuko Sho
Thiourea derivatives described in 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., may also be contained. Further, the pH of the bleach-fix solution is generally 4.0 to 8.0, particularly preferably 5.0 to 7.0, when used. The above bleach or bleach composition refers to both a bleaching solution as a working or replenishing solution and a bleach-fixing agent formulation for preparing a bleaching solution as a working or replenishing solution. In the case of two or more liquid preparations,
Regardless of the above pH range, the pH of the liquid agent containing the ferric ion complex salt can be further increased. The object of the present invention can also be achieved by adding the compound represented by formula (a) or (b) to the above bleaching solution or bleach-fixing solution, but in this case, the amount added is 1×10 ^{- 3} mol/~2×10 ^-1 mol/,
Preferably 1×10 ^-2 mol/~4×10 ^-2 mol/
, 1×10 ^-3 mol/~2×10 ^-1 in bleach-fix solution
mol/, preferably 1×10 ^-2 mol/~4×
10 ^-2 mol/. 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 are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds generally have a concentration of about 0.1 g to about 30 g per color developer,
More preferably, about 1 g per color developer 1
- Use at a concentration of approximately 15 g. Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-oxy-toluene, 2-amino-
Included are 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, examples of particularly useful compounds include:
N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-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-methoxyethyl)-N-ethyl-
Examples include 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 may also optionally contain alkaline agents such as potassium, 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 more, 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 coupler-containing multilayer negative color photographic material or It can be used particularly advantageously when processing color print photographic materials or when processing color photographic materials made for reversal color processing, as well as color X-ray photographic materials, single-layer special Color photographic materials can also be processed. Alternatively, there is no problem in processing the coupler in the presence of the developer. The silver halide photographic light-sensitive material applicable to the present invention uses an internal development method (for example, U.S. Pat. No. 2,376,679, U.S. Pat. No. 2,801,171
In addition to external development methods in which a color former is contained in the developer (for example, U.S. Pat.
2252718, 2592243, 2590970, 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 naphthol or phenol structures and form indoaniline dyes by coupling;
Magenta coloring agents include those having a skeletal structure of a 5-pyrazolone ring having an active methylene group;
Examples of yellow coloring agents include those having a substituent at the coupling position, such as benzoylacetanilide, pivalyl acetanilide, and acylacetanilide structures having active methylene chains;
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 coated. First layer (red-sensitive emulsion layer) Silver iodobromide emulsion containing 10 g of silver halide and 5 g of gelatin per 100 g of emulsion (silver iodide 5 mol%)
For 1000g, 500g of gelatin solution emulsifying and dispersing cyan coupler (C-1) (molar ratio of silver and coupler is 7:1), 1% aqueous solution of stabilizer (A-1)
50 c.c., 50 c.c. of a 1% aqueous solution of coating agent (T-1), and 20 c.c. of a 2% aqueous solution of hardener (H-1) were added to an emulsion solution with a dry film thickness of 4μ. I applied it to make it look like this. Second layer (intermediate layer) 100g of gelatin aqueous solution in which color mixing inhibitor (A-2) was emulsified and dispersed in 1000g of 5% gelatin aqueous solution,
A gelatin solution containing 50 c.c. of a 1% aqueous solution of the coating agent (T-1) and 20 c.c. of a 2% aqueous solution of the hardening agent (H-1) was applied to give a dry film thickness of 1 μm. Third layer (green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 5 mol%) containing 10 g of silver halide and 5 g of gelatin per 100 g of emulsion.
For 1000g, add 700g of gelatin solution in which magenta coupler (C-2) is emulsified and dispersed (molar ratio of silver to coupler is 7:1), and 1% aqueous solution of stabilizer (A-1).
50c.c., 50c.c. of 1% aqueous solution of coating agent (T-1) and 20c.c. of 2% aqueous solution of hardener (H-1) were added to make an emulsion solution with a dry film thickness of 4μ. It was applied like this. Fourth layer (yellow filter layer) 5% gelatin aqueous solution in which colloidal silver is dispersed
1% aqueous solution of coating agent (T-1) for 1000g
100 c.c. and 20 c.c. of a 2% aqueous solution of hardener (H-1) was added so that the amount of silver coated was 0.5 mg/100 cm ² . Fifth layer (blue-sensitive emulsion layer) Silver iodobromide emulsion containing 10 g of silver halide and 5 g of gelatin per 100 g of emulsion (silver iodide 5 mol%)
For 1000 g, add 500 g of gelatin solution emulsified and dispersed with yellow coupler (C-3) (molar ratio of silver to coupler is 7:1), 50 c.c. of 1% aqueous solution of stabilizer (A-1), coating agent ( An emulsion solution containing 50 c.c. of a 1% aqueous solution of T-1) and 20 c.c. of a 2% aqueous solution of a hardener (H-1) was applied to give a dry film thickness of 4 μm. Sixth layer (protective layer) 1% coating agent (T-1) in 5% gelatin aqueous solution
Aqueous solution 100 c.c., 1% aqueous solution of hardener (H-1) 20
A gelatin solution containing cc was applied to give a dry film thickness of 1 μm. [Emulsification method: Dissolve 75 g of cyan coupler (C-1) in a mixture of 100 c.c. of dibutyl phthalate and 200 c.c. of ethyl acetate, and emulsify this in 600 g of a 10% gelatin aqueous solution together with a dispersion aid. ] [Emulsification method Emulsification is carried out in the same manner as in the case of cyan coupler (C-1), except that 75 g of magenta coupler (C-2) is dissolved instead of cyan coupler (C-1). ] [Emulsification method: Emulsify in the same manner as for cyan coupler (C-1) except that 90 g of yellow coupler (C-3) is dissolved instead of cyan coupler (C-1). ] Emulsification recipe: Dissolve 100g of color mixing inhibitor (A-2) in a mixture of 200c.c. of dibutyl phthalate and 200c.c. of ethyl acetate.
This was emulsified in 500 g of a 10% aqueous gelatin solution together with a dispersion aid. The color reversal film obtained in this manner is exposed appropriately, and is subjected to the following development process using various pre-baths to which the compound represented by general formula (a) or (b) is added. Developed. First development 43℃ 2 minutes First stop 40℃ 20 seconds Washing 〃 40 seconds Second development 46℃ 2 minutes 15 seconds Before bathing 40℃ 15 seconds Washing 〃 5 seconds Bleaching 〃 45 seconds Fixing 〃 40 seconds Water Washing 25 seconds Stable 20 seconds 1st developer Water 800ml Quodrafos 2.0g Anhydrous sodium bisulfite 8.00g Phenidone 0.35g Anhydrous sodium sulfite 37.0g Hydroquinone 5.50g Anhydrous soda 28.2g Rodan soda 1.38g Sodium bromide 1.30g Iodination Potassium (0.1% solution) 13.0ml Add water 1.00 PH 9.90 1st stop solution Water 800ml Glacial acetic acid 30.0ml Caustic soda 1.65g Add water 1.00 PH 3.50 2nd developer

【table】 Before bath

[Table] Bleach solution Water 800ml Sodium persulfate 60g Sodium chloride 30g Phosphoric acid aqueous solution (85% by weight) 11.8ml Caustic soda 6.4g Add water 1.00 PH 2.7 Fixing solution Water 600ml Ammonium thiosulfate aqueous solution (58% by weight) 169ml Anhydrous sodium sulfite 11.5g Ethylenediaminetetraacetic acid disodium salt 0.5g Sodium acetate anhydride 12g Glacial acetic acid 9ml Add water 1.00 PH 5.5 Stable bath Water 800ml Formalin water (37.5% by weight) 6.0ml Add water 1.00 Each of the above developed The amount of silver remaining in the film sample was measured by X-ray fluorescence analysis. The results are as follows.

[Table] As described above, the film treated with the pre-bath containing the compound of the present invention was 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 prebath containing the compound of the present invention was treated with the prebath not containing the compound of the present invention. A much clearer and more vivid color image was obtained compared to the processed film. Bleach solution: Aqueous ammonia (28%) 5ml Ethylenediaminetetraacetic acid 10g Ferric ethylenediaminetetraacetic acid ammonium salt/dihydrate 130g Potassium bromide 100g With water 1 PH5.60 Example 3 The following was applied on the undercoated cellulose triacetate film. A color negative film sample was prepared by sequentially applying the first layer to the 11th layer starting from the first layer. 1st layer (antihalation layer) 2nd gelatin layer containing black colloidal silver (intermediate layer) 3rd gelatin layer containing an emulsion of 2,5-di-t-octylhydroquinone (low-sensitivity red-sensitive emulsion layer) Low-sensitivity silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.8 μ, gelatin 70 g/Kg emulsion) Coated silver amount 2.2 g/ ^m2 Sensitizing dye 3.0×10 ^-4 mol increase per 1 mol silver Sensitive dye 0.8×10 ^-4 mol per mol of silver Coupler A 160×10 ^-5 mol/m ² Coupler B 19×10 ^-5 mol/m ² DIR coupler F 2×10 ^-5 mol/m ² 4th layer (High-sensitivity red-sensitive emulsion layer) High-sensitivity silver iodobromide emulsion (silver iodide 5 mol%, average grain size 1.2μ, gelatin 70g/Kg emulsion)
Coated silver amount 2.4 g/m ² Sensitizing dye 1.5×10 ^-4 mol per 1 mol silver Sensitizing dye 0.4×10 ^-4 mol per 1 mol silver Coupler A Coated amount 27×10 ^-5 mol 5th layer ( 6th layer (intermediate layer) same as 2nd layer (low-sensitivity green-sensitive emulsion layer) low-sensitivity silver iodobromide emulsion (silver iodide 7 mol%, average grain size 0.8μ, gelatin 70g/Kg emulsion)
Coated silver amount: 1.9 g/m ² Sensitizing dye: 4.0 x 10 ^-4 mol per mol of silver Sensitizing dye: 0.5 x 10 ^-4 mol per mol of silver Coupler C 74 x 10 ^-5 mol/m ² Colored coupler D 12×10 ^-5 mol/m ² DIR coupler F 3.6×10 ^-5 mol/m ² 7th layer (high sensitivity green-sensitive emulsion layer) High sensitivity silver iodobromide emulsion (silver iodide 8 mol %, average grain size 1.2μ, gelatin 70g/Kg emulsion)
Coated silver amount: 1.8 g/m ² Sensitizing dye: 2.0 x 10 ^-4 mol per mol of silver Sensitizing dye: 0.3 x 10 ^-4 mol per mol of silver Coupler C 22 x 10 ^-5 mol/m ² Colored coupler D 4×10 ^-5 mol/m ² 8th layer (yellow filter layer) 9th gelatin layer containing an emulsified dispersion of yellow colloidal silver and 2,5-di-t-octylhydroquinone (low-sensitivity blue-sensitive emulsion layer) Low-sensitivity silver iodobromide emulsion (silver iodide 7 mol%, average grain size 0.8μ, gelatin 70g/Kg emulsion)
Coated silver amount 0.8 g/m ² Coupler E 150×10 ^-5 mol/m ² DIR coupler F 2×10 ^-5 mol/m ² 10th layer (high-sensitivity blue-sensitive emulsion layer) High-sensitivity silver iodobromide emulsion ( Silver iodide 8 mol%, average grain size 1.3μ, gelatin 70g/Kg emulsion)
Coated silver amount: 0.9 g/m ² Coupler E 22×10 ⁻⁵ mol/m ² Eleventh layer (protective layer) Gelatin layer Each layer contains a gelatin hardener, coating aid, etc. in addition to the above composition. Materials used; Sensitizing dye; Anhydro 5,5'-dichloro-
3,3'-disulfopropyl-9-ethyl-thiacarbocyanine hydroxide pyridium salt; anhydro-9-ethyl-3,3'-
Di-(3-sulfopropyl)-4,
5,4',5'-dibenzothiacarbonanine hydroxide triethylamine salt; anhydro-9'-ethyl-5,5'-
Dichloro-3,3'-disulfopropyloxacarbocyanine sodium salt; anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl-3,
3'-di(sulfopropoxyethoxyethyl)-imidazolocarbocyanine hydroxide sodium salt coupler A; 1-hydroxy-N-[γ-(2,4
-di-t-amylphenoxypropyl)]-2-naphthamide coupler B; 1-hydroxy-4-{2-(2-hexyldecyloxycarbonyl)phenylazo}-2-{N-(1-naphthal) }-naphthamide coupler C; 1-(2,4,6-trichlorophenyl)-3-[α-(2,4-di-t
-Amylphenoxy)acetamide]benzamide-5-pyrazolone coupler D; 1-(2,4,6-trichlorophenyl)-3-[3-{α-2,4-di-t-amylphenoxy)acetamide}benzamide]- 4-Methoxyphenylazo-5-pyrazolone coupler E; α-(2,4-dioxo-5,5'-
dimethyloxazolidinyl)-αpiparoyl-2-chloro-5-{α-
(2,4-di-t-amylphenoxy)butyramide}acetanilide coupler F; α{5(6)-(3-methyl-2-benzothiazolylideneamino)-1-benzotriazolyl}-α-(4 -octadecyloxybenzoyl)-2-
Ethoxy-acetanilide Each of the above coupler emulsions was prepared by dissolving the coupler in a dibutyl phthalate and tricresyl phosphate mixture, solhitan monolaurate,
Funnel oil and sodium dodecylbenzenesulfonate are dispersed in an O/W type in a gelatin solution as dispersing emulsifiers. The photographic element was exposed to light (1/50 second, 10 C.MS) and then processed at 38° C. according to the processing steps described below. 1 Color development 3 minutes 15 seconds 2 Pre-bath 30 seconds 3 Bleaching 2 minutes 4 Fixing 3 minutes 15 seconds 5 Washing 2 minutes 10 seconds 6 Stability 30 seconds The composition of the processing solution used in each step is as follows. Ta. color developer

[Table] Bleach solution Water 800ml Sodium persulfate 70g Sodium chloride 25g Phosphoric acid aqueous solution (85% by weight) 11.8ml Caustic soda 6.4g With water 1 PH2.7 Fixing solution Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70 %) 175.0ml Sodium bisulfite 4.6g Add water 1 PH6.6 Stabilizing solution Formalin water (40%) 8.0ml Add water 1 Pre-bath Glacial acetic acid 10ml Sodium sulfite 12g Compound (2) Add water 1 Others The development process described above was carried out using a prebath having the same composition as above except that compound (2) was not added thereto. Sample 1 2 Compound of the present invention No Compound (2) Added amount / 2 × 10 ^- 2 mol / Residual silver amount 29 μg/cm ² 8 μg/cm ² Bleaching can be achieved in a significantly shorter time by using the compound of the present invention in the pre-bath It was done. Preferred embodiments of the present invention are as follows. 1. An embodiment in which persulfate is used as a bleaching agent 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 ethylenediaminetetraacetic acid ferric complex salt is used as a 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 general formula (a) or (b) in the claims. 5. An embodiment in which the pre-bath is placed immediately before the bleaching bath or bleach-fixing bath in 4 above.

Claims (1)

[Scope of Claims] 1. Before bleaching, pretreatment is performed with a bath containing a compound represented by general formula (a) or (b), or a method containing a compound represented by general formula (a) or (b). 1. A method for bleaching silver halide color light-sensitive materials, which uses a bleaching solution or a bleach-fixing solution, and the bleaching agent is a ferric ion complex or a persulfate. General formula (a) General formula (b) Here, A represents an optionally substituted amino group or nitrogen-containing heterocyclic ring. R ¹ represents a hydrogen atom or a carboxyl group. R ² is a monovalent metal atom,
Indicates an ammonium group, an optionally substituted alkyl group, or a group represented by [Formula] or [Formula]. R ³ and R ⁴ each represent a hydrogen atom or an optionally substituted alkyl group. m is 1 or 2, n is 1~
Indicates an integer of 4.