JPS5945145B2 - Bleaching method for color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for photographically processing a silver halide color photographic light-sensitive material, and more particularly to a color photographic rapid bleaching method in which environmental pollution caused by wastewater can be ignored.

In the photographic processing of silver halide color photographic light-sensitive materials, the light-sensitive material (the silver halide photographic emulsion may be fogged in advance) is usually developed with an aromatic primary amine in the presence of a color-forming coupler. After developing with a developer containing a main agent to obtain a color image, the developed silver produced at the same time is rehalogenated by bleaching and removed together with undeveloped silver halide by fixing (or bleach-fixing).

Conventionally, red blood salt (ferricyanide), ferric chloride, aminopolycarboxylic acid ferric complex salt, etc. have been mainly used as bleaching agents.

However, if these bleaches are mixed into wastewater, they cause environmental pollution, and to prevent this, it is necessary to recover these bleaching agents. Bleaching baths used in processing color photographic materials must not destroy dyes or dye intermediates produced during color development. The use of bleaching powder and sulfamic acid as a bleaching agent for color photographic materials was established in 1973.
No. 11068, this bleaching agent causes destruction of pigments, leading to changes in hue and loss of density of color images. In addition, this bleaching method causes pollution problems due to bad odors caused by the bleaching powder. Although it was known to use free chlorine in the bleaching process of color photographic materials, it had serious drawbacks and could not be put to practical use.

One possible method for silver bleaching color photographic materials is to use free bromine. Free bromine can be generated by electrolytically oxidizing bromide ions in an aqueous solution. When an aqueous solution containing bromide ions is electrolyzed using a carbon anode, an oxidation reaction occurs at O, 8V (vs. saturated Kanaga electrode) or higher, and an oxidizing agent (Br2) that can bleach silver.
is provided. However, Br2 has a bad odor and is toxic, and if it is tried to be used as a photographic bleaching agent, its oxidizing power is too strong, leading to destruction of pigments and gelatin crosslinks, so it cannot be used as a photographic bleaching agent. It was extremely difficult. The first object of the present invention is to provide a method for bleaching color photographic materials in which environmental pollution caused by wastewater can be ignored.

A second object of the present invention is to provide a method for bleaching color photographic materials that does not require recovery of bleaching agents in order to prevent environmental pollution.

A third object of the present invention is to provide a method for bleaching color photographic materials that causes less damage such as decomposition of dyes.

The above objects of the present invention are to achieve exposure and development (black and white development and/or
When bleaching a silver halide color photographic material that has been subjected to color development or color development, bromine (BrOmine) is removed by electrolytic oxidation.
bromine generated by electrolyzing an aqueous solution containing a water-soluble compound that generates This was effectively achieved by a method in which bleaching is carried out using a bleaching solution having bleaching activity obtained by coexisting with the bleaching agent.

The bleaching solution according to the present invention does not cause destruction of dyes or gelatin crosslinks.

This is probably due to the formation of a relatively stable reaction intermediate between the amino alcohol and the bromine generated by electrolysis, and this intermediate is presumed to act as a good bleaching agent. Water-soluble compounds that generate bromine through electrolytic oxidation can be selected from inorganic and organic compounds containing bromine, such as alkali metal bromide salts (e.g., sodium salts and potassium salts) and water-soluble compounds such as ammonium bromide. Bromides, water-soluble bromates (counter ions include, for example, the above-mentioned alkali metal ions and ammonium ions), tetraalkylammonium bromides (eg, tetramethylammonium bromide, tetraethylammonium bromide, etc.), and the like.

Among these, salts that dissociate bromide ions in an aqueous solution, such as alkali metal bromide salts and ammonium bromide, are preferred.
Particular preference is given to using potassium bromide. Bromide ions are a source of bromine, and also serve as counter ions for silver ions produced by bleaching, thereby acting as a promoter of the bleaching reaction.

The specific amount of the bromine generating compound added is approximately 5.times.10@-3 to 3 mol per 11 of the electrolytic solution. The preferred amount to be added can be appropriately determined by conventional experimental procedures. A typical water-soluble compound that generates bromine through electrolytic oxidation is a salt that releases bromide ions in an aqueous solution, so this will be described below as a representative "bromide ion."

The amino alcohol used in the present invention is preferably represented by the following general formula (1).

R1-NH-R2-0H (1) In the formula, R2 represents a divalent aliphatic group represented by R3 or R3OR4.

R3 and R4 each represent the same or different alkylene groups. R1 represents a hydrogen atom, an optionally substituted alkyl group, or an aryl group (Aryl). R3 and R
The alkylene group represented by 4 preferably has 2 to 5 carbon atoms, and the carbon chain may have a branch.

When substituted, a hydroxy group, an amino group, a carboxy group, a sulfo group, a halogen atom, etc. can be included as a substituent. When R1 represents an alkyl group,
The alkyl group preferably has 1 to 5 carbon atoms, and the carbon chain may have a branch. In the case of substituted alkyl groups and aryl groups, substituents include hydroxy group, amino group,
It can have a carboxy group, a sulfo group, a halogen atom, etc. Compounds in which the NH group and the OH group of the general formula (I) are separated into 2 to 3 carbon atoms are preferable because the effects of the present invention are large.

Specific examples of the amino alcohol used in the present invention are shown below.

It is appropriate that the amino alcohol be contained in an amount of about 1 x 10-4 to 5 mol per 11 mols of the aqueous solution containing it (
The preferred amount can be determined as appropriate).

In addition, water-soluble salts such as sulfates, nitrates, carbonates, phosphates, and borates may also be added to the aqueous solution. The ratio of bromide ion to amino alcohol used is preferably such that the amount of coexisting amino alcohol is greater than the amount of bromine generated. The pH of the bleaching solution is suitably about 4 to 9.5, preferably 6 to 8.5.

Next, referring to the material of the electrode used for electrolysis, the anode may be any electrically conductive material or semiconductor material that does not dissolve during electrolysis, such as carbon (including graphite).

(may be plate-like or fibrous), platinum, titanium alloy (alloy ingredients include Ti and others AlsCrlFesMnsMOLV)
(selected from metals such as). As the cathode, any corrosion-resistant and electrically conductive material may be used, but stainless steel (components include Fe, Cr, and N) may be used as the cathode.
Selected from metals such as l. SUS32 is preferred. )
, platinum, titanium alloys, etc. are suitable. The electrolytic cell may have a diaphragm, but it is not necessary. It is preferable to mix the liquids during electrolysis. The current used for electrolysis is approximately 0.1-20A
/Dm2 is appropriate.

The current should be passed within a range that does not cause an excessive rise in temperature due to heat generation. An aqueous solution containing bromide ions and amino alcohols has no activity unless electrolyzed, but becomes bleaching active through electrolysis and can be used as a bleaching solution.

Sufficient bleaching activity can be provided by using an amount of electricity of 96,500 clones or more per mole of silver in the sensitive material during electrolysis. The upper limit of this amount of electricity ultimately depends on the amount of photosensitive material to be bleached. It is convenient for the night temperature during electrolysis to be approximately the same as the temperature required for the bleaching solution. but,
These temperatures do not need to be the same. The liquid obtained by electrolysis has only a pale yellow color and only a slight bromine odor, so there is no concern about pollution.

Amino alcohols, bromide ions, and PH buffers (anything that can be used as a PH buffer for bleaching solutions) can be used.

For example, any known material that can be used for this purpose can be used. For example, phosphate ion, borate ion, bicarbonate ion, etc. ) When an aqueous solution consisting of
At the end, both reach a saturation value. The amount of active bromide also increases, but reaches a saturation value. Therefore, the solution after electrolysis for a certain period of time contains a stable amount of oxidizing agent, and the pH and redox potential are also stable, so that a stable bleaching solution can be obtained. Further, after a certain period of time (for example, about one day) has passed after the electrolysis is stopped, the active bromide loses its bleaching edge and becomes bromide ions. When electrolysis is started again, active bromide is obtained, and the cycle can be repeated. That is, according to the present invention, a stable bleaching solution can be obtained simply by replenishing the bromide ions, amino alcohols, etc. that have been reduced by the bleaching treatment and continuing electrolysis. Moreover, even if the processing solution deactivated after stopping the electrolysis or bleaching treatment is disposed of, it hardly causes environmental pollution. Further, in addition to bromide ions, amino alcohols, and pH buffering agents, anticorrosive agents (for example, alkali metal salts of nitric acid, such as sodium nitrate and potassium nitrate) may also be present. Below, an apparatus for carrying out electrolysis in the method of the present invention will be explained.

First, a so-called "single tank type" device in which the electrolyzer and the sensitive material processing tank are in the same tank will be explained. The electrolytic cell has an anode and a cathode each connected to a DC power source, and equipment necessary for processing sensitive materials (e.g. film transport rollers, hangers, etc.)
and an electrolytic solution (bleaching solution), as well as stirring means (for example, liquid circulation gas aeration, stirring by a propeller, etc.), a replenisher addition device to maintain a predetermined liquid composition, an overflow liquid outlet, etc. that are normally used in automatic developing machines. The attached device can be an accessory device.

(Hereinafter referred to as Embodiment 1) Next, a so-called "two-tank type" apparatus (Embodiment 2) in which an electrolytic cell and a sensitive material processing tank are provided separately will be described. The electrolytic cell consists of an anode, a cathode, and an electrolytic solution (bleaching solution), each connected to a DC power source, and may also be provided with stirring means (for example, a propeller or a liquid circulation pump).

On the other hand, the sensitive material processing tank is also a container equipped with a stirring means, and includes a pipe with a circulation pump installed in the middle (this is located relatively below the tank) and another pipe (this is located relatively above). It is connected to the electrolytic cell via two pipes. These two pipes allow the electrolyte (bleaching solution) to circulate between both tanks. A circulation pump may be installed in the middle of the upper pipe. One aspect of the shape of the electrode used in the above two embodiments is as follows.

Anode: In order to prevent the generated Br2 from scattering before it reacts with the amino alcohols, and to reduce excess Br to Br- again and obtain a certain amount of oxidizing agent, the anode is placed below the cathode. Moreover, it is installed parallel to the bottom surface of the electrolytic cell, and only the surface of the parallel part is used as a conductive part, and the vertical part (conducting wire) is shielded with an organic synthetic resin.

Cathode: In order to prevent the generated hydrogen gas from adsorbing to the electrode and increasing the electrical resistance, it is not parallel to the bottom of the electrolytic cell, but has an inclination of about 45 degrees, and a groove is provided on the surface to prevent the electrode from adsorbing to the electrode. Facilitates the rise and desorption of hydrogen gas from

Next, an apparatus (embodiment 3) which also belongs to the two-tank type will be explained.

An aqueous solution containing bromide ions and an electrode (electrolytic tank) and an aqueous solution containing amino alcohols (sensitive material processing tank)
is separated through a porous partition wall, and the generated Br2 (
Similarly, H2) can be introduced into an aqueous solution containing amino alcohols through the partition wall to form a bleaching solution.

The partitions used in this method are continuous microporous partitions that do not allow ions to pass through but allow gases to pass through, and are made of, for example, poly(tetrafluoroethylene) or poly(tetrafluoroethylene) and polyethylene, polypropylene, polyvinyl chloride. It consists of a mixture with polymers such as.
In the latter case, the content of poly(tetrafluoroethylene) is preferably 50 percent or more. Average pore diameter is approximately 0.2~
100 microns is suitable, but 0.5 to 50 microns is preferred. The thickness of the partition wall is approximately 0.01 to 5 mm, preferably 0.1 to 2 mm. Such porous partition walls are described in JP-A-46-7284, JP-B No. 42-13560, JP-A-49-41265, and US Pat. Nos. 3,315,020 and 3,664,915. When the partition body is tubular, the inner diameter is approximately 0.4 to 10 mm. is suitable, but about 1 to 10 mm is preferred. When using this method, the pH of the electrolyte is preferably 7 or less, especially about 5 to 7.
is preferred. On the other hand, it is appropriate for the aqueous solution containing amino alcohols to have a value of about 4 to 9.5, especially 6.0 to 9.5.
It is preferable to set it to 8.5. At this time, it is preferable that the electrolytic cell containing the electrolytic solution is sealed during electrolysis.This is to prevent the bad smell of Br2 generated, and also to prevent the inside of the electrolytic cell from being contaminated due to the generation of hydrogen gas. This is because a pressurized state is created, which allows Br2 and hydrogen gas to easily pass through the partition wall. The electrolytic cell, electrode shape, and sensitive material processing bath described above are representative embodiments of the present invention, and the present invention is not limited thereto.

In the bleaching method of the present invention, the bleaching solution further contains primary amines (e.g. ethylamine, ethylenediamine, sulfamic acid), secondary amines (e.g. dimethylamine, diethylamine), amides (e.g. succinimide, acrylamide, benzenesulfonamide) or urea derivatives (e.g. urea, dimethylolurea, hydantoin or N-bromide compounds (e.g. N
- Bromsuccinimide), etc.

The method of the present invention uses color negative film, color paper,
It can be applied to any processing of silver halide glass photographic materials such as color positive films, color reversal films, and silver dye bleaching materials. In the method of the present invention, the processing steps for color negative film, color positive film, color paper, etc. exposed to 6 images are usually 6 (1) color development → stop → bleach → water washing → fixing → water washing → stabilization → drying, (2) color development. Development → Stop → Bleach → Fix → Wash → Stabilize → Dry. Or (3
) Color development → stop and fix → bleach → fix → wash → stabilize → dry.

In the steps (1) to (3), a pre-bath, hardening bath, etc. may be further provided before color development, and a stabilizing bath, washing with water after bleaching, etc. can be omitted. On the other hand. The processing process for color reversal film is usually (4) black and white development → stop → water washing →
Power brush → Wash with water → Color development → Stop → Wash with water → Bleach → Wash with water →
Fixing → washing → stabilization → drying, or (5) black and white development → stop →
Washing with water → Power brush → Washing with water → Color development → Stop → Washing with water → Bleaching →
The basic process is fixation → washing with water → stabilization → drying.

In steps (4) and (5), a pre-bath 6, a pre-hardening bath, a neutralizing bath, etc. can be further provided. Furthermore, washing with water after bleaching in stabilizing bath 2 can be omitted. The force brush bath can be replaced by re-exposure, or the force brush bath can be omitted by adding a force brush agent to the color developer. In the photographic processing method of the present invention, the above (1) to (5):
Although the steps shown are useful, the invention is not limited to these steps.

The color developer used in the present invention has the composition of a general color developer containing an aromatic primary amine developer.

Preferred examples of aromatic primary amine color developing agents are p-phenylenediamine derivatives as shown below. N,N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5-(N-ethyl-N-laurylamino)toluene. 4-[N-ethyl-
N(β-hydroxyethino(ha)amino)aniline.2
-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline, N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-amino described in U.S. Pat. No. 2,193,015 Aniline, US Patent 25
N-(2-amino-5-diethylaminophenylethino(c)methanesulfonamide.N, described in No. 92364)
N-dimethyl-p-phenylenediamine, US Patent 36
4-amino-3-methyl-N-ethyl-N-methoxyethylaniline described in No. 56950, No. 3698525, etc. 4-amino-3-methyl-N-ethyl-N-β
monoethoxoethylaniline and 4-amino-3-methyl-N-ethyl-N-β-butoxyethylaniline,
Preferred representative examples include these salts (eg, sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc.).

The color developer may contain other known developer components. For example, as an alkali agent or buffering agent, 6 caustic soda, 2 caustic potash, 6 sodium carbonate, potassium carbonate, tertiary sodium phosphate, or 1 acid, 1 acid, 1 sand, etc. may be used alone. Or used in combination. In addition to the above additives, hydrogen phosphate 2
Various salts are used, such as sodium or potassium dihydrogen hexaphosphate or sodium, sodium bicarbonate or potassium, phosphoric acid, alkali nitrate, alkali sulfate, and the like. If necessary, any development accelerator can be added to the color developing solution. For example, various pyridinium compounds and other cationic compounds represented by US Pat. 6 Japanese Patent Publication No. 44-9504, US Patent No. 2,533,990, US Patent No. 2,531,832, US Patent No. 2,950,970. Nonionic compounds such as polyethylene glycol, derivatives thereof, and polythioethers described in U.S. Patent No. 2,577,127; organic solvents and organic amines (e.g., ethanolamine, ethylenediazine, diethanolamine) described in Japanese Patent Publication No. 44-9509 and Pelkey Patent No. 682,862; etc., and other L. F. A. Mas
“PhOtOgraphicPrOcessin” by On
gChemistry” P4O~43 (FOcalP
ress-LOndOn-1966) can be used.

In addition, benzyl alcohol and phenylethyl alcohol described in US Pat. No. 2,515,147, Journal of the Photographic Society of Japan, Vol. 14. Pyridine, ammonia, hydrazine, amines, etc. described on page 74 (1952) are also useful development accelerators. In addition, sulfites (eg, sodium sulfite, potassium sulfite, potassium bisulfite, or sodium bisulfite), which are usually used as preservatives, hydroxylamine, ascorbic acid, pentose, hexose, etc. can be added.

In the present invention, any antifogging agent may be added to the color developing solution if necessary.

Antifoggants include potassium bromide and sodium bromide 6.
Alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, and 5-nitroisointazole. 5-Methylbenzotriazole. 5-Nitrobenzotriazole. Nitrogen-containing heterocyclic compounds such as 5-chlorobenzotriazole and 1
-Phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole. Mercapto-substituted zero ring compounds such as 2-mercaptobenzothiazole, as well as mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. A 6-nitrogen-containing zero-ring compound is preferred, and a nitrogen-containing zero-ring compound that is not mercapto-substituted is particularly preferred. The amount of the antifoggant to be added is within the range of approximately 6 to 5, preferably 5 to 19, per 11 parts of the color developing solution. Furthermore, polyphosphoric acid compounds represented by sodium hexametaphosphate, sodium tetrapolyphosphate, sodium tripolyphosphate, or potassium salts of each of the above polyphosphoric acids, phosphonic acid, phosphonocarboxylic acid, α-amino acids, ethylenediaminetetraacetic acid, nitrilotriacetic acid 6-cyclohexane. Aminopolycarboxylic acids represented by diaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, etc. can be used as the water softener.

The amount added varies depending on the hardness of the water used, but is usually about 0.5 to 1 f1/l. Other calcium and magnesium hiding agents can also be used in photographic processing solutions. This is J. “Beigis” by Willems
cheChemischeIndustrie”, 21
Volume, 325 pages (1956) and Volume 23, 110
Details are given on page 5 (1958).

In the case of reversal color processing, competing couplers, force brushing agents and compensating developers may also be added to the color developer.

Citrazic acid, J acid as competitive couplers. H acids and the like are useful.

For example, U.S. Patent No. 2742832, Japanese Patent Publication No. 44-95
No. 04, No. 44-9506, No. 44-9507, U.S. Patent No. 3645-737, No. 3560212, No. 3
Compounds described in No. 645737 and the like can be used. Power brushing agents include alkali metal borohydrides (e.g. sodium borohydride), amine borane (e.g. t-butylamine borane). Tin-aminopolycarboxylic acid complex salt, tin-pyrophosphate complex salt, tin-tetrapolyphosphate complex salt, hexatin-hexametaphosphate complex salt, ethylenediamine, etc. can be used.

Other compounds described in Japanese Patent Publication No. 47-38816 are also useful. As a compensating developer, p-aminophenol is used. N-benzyl-p-aminophenol, 1-phenyl-3-pyrazolidone, etc. can be used.

Others, such as Special Publication No. 45-41475, No. 46-1
Compounds described in No. 9037 are also useful. The value of the color developing solution is in the range of about 7 to 14, and preferably in the range of about 8 to 13.

The processing method of the present invention is applicable to color photography processes in which dye-forming couplers are included in the light-sensitive material, such as U.S. Pat.
Not only can it be applied to the methods described in US Pat. No. 027, No. 2376679, and US Pat.
It is also applicable to the methods described in No. 2,590,970, and No. 2,592,243.

However, at present, the former method is mainly used.

When a dye-forming coupler is included in a light-sensitive material, a multilayer light-sensitive material is generally used, in which the coupler remains in a given layer and does not diffuse into other layers during manufacturing, storage, and processing steps. This is desirable. In carrying out the present invention 6
If a coupler is used, the coupler may be a four-equivalent coupler or a two-equivalent coupler.

Further, at least a part thereof may be a dynamic coupler for color correction, a colorless coupler, or a coupler that releases a development inhibitor during development (so-called DIR coupler). As the yellow color-forming coupler, a 6-open chain ketomethylene coupler can be used. Among these, benzoylacetanilide and piparoylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include U.S. Pat.
No. 06, No. 3408194, No. 3551155, No. 3582322, No. 3725072, No. 38948
No. 75, West German Patent Publication No. 1547868, West German Patent Application (0LS) No. 2213461, No. 2219917, No. 2261361, No. 2263875, No. 24140
There are those described in No. 06, etc.

As the magenta coloring coupler, 5-pyrazolone compounds are mainly used, but intazolone compounds and cyanoacetyl compounds can also be used. An example is 6 U.S. Patents 2
No. 600788, No. 2983608, No. 306265
No. 3, No. 3127269, No. 3311476, No. 3
No. 419391, No. 3476560, No. 351942
No. 9, No. 3558319, No. 3582322, No. 3
No. 615506, West German Patent No. 1810464, West German Patent Application (0LS) No. 2408665, No. 2418959, No. 2424467, Japanese Patent Publication No. 1973-6031. Same 4
4-2016, etc.

Phenol or naphthol derivatives are mainly used as cyan color-forming couplers. Specific examples thereof include U.S. Pat.
No. 93, No. 2521908, No. 2895826, No. 3034892, No. 3311476, No. 33868
No. 30, No. 3458315, No. 3476563, No. 3583971, No. 3591383, JP-A No. 1973-
There is one described in No. 78905.

others. Specific examples of DIR couplers and other "compounds that release development-inhibiting compounds" include U.S. Pat.
No. 27554, No. 3617291, No. 3632345
No. 3701783, No. 3790384, British Patent No. 953454, West German Patent Application (0LS) 24140
No. 06, No. 2417914, No. 2417945, No. 2454301, No. 2454329, U.S. Patent 32
It is described in No. 97445, No. 3379529, etc.

Others: JP-A-51-102636, JP-A No. 51-265
No. 41, No. 50-159336, No. 51-20826
No. 51-26034, patent application No. 114445-1973
No. 50-1792, No. 50-70592, No. 5
No. 0-96435, No. 50-118029, No. 50-
Couplers described in each specification of No. 118540 can also be used.

Two or more of the above couplers may be used in the same layer in order to satisfy the characteristics required for photosensitive materials. However, it is of course possible to add the same coupler to two or more different layers.

These couplers are generally dispersed in the silver hexahalide photographic emulsion layer with a solvent of appropriate polarity. Useful solvents include 6-tri-0-cresyl phosphate, trihexyl phosphate, dioctyl butyl phosphate, dibutyl phthalate, diethyl laurylamide, 2,4-diallylphenol, octyl benzoate, and the like. Typical color image forming substances for the silver dye bleaching photosensitive material processed in the present invention include, for example, azo dyes.

The color light-sensitive material to be photographically processed by the method of the present invention has at least one silver halide emulsion layer on a support. Red-sensitive silver halide emulsion layer 2
It has a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer.

More specifically, a red-sensitive silver halide emulsion layer containing a cyan image-forming coupler and a green-sensitive silver halide emulsion layer containing a magenta image-forming coupler are usually formed on a support. Each has at least one blue-sensitive silver halide emulsion layer containing a yellow imaging coupler. Such photographic elements may include non-light-sensitive photographic layers (e.g. 6 anti-halation layers, 6 interlayers to prevent color mixing, etc., a yellow filter layer, a protective layer, etc.). It's good to wear. Also. There is no particular restriction on the arrangement order of the red-sensitive layer, green-sensitive layer and blue-sensitive layer. The silver halide photographic emulsion may be of the 6-surface latent image type or the internal latent image type, and may be manufactured by a conventionally known method. The stabilizing bath contains image stabilizers (e.g. formaldehyde), surfactants (e.g. polyethylene oxide), hardeners (e.g. potassium alum), and ultraviolet absorbers (e.g. bistriacylaminostilbenes) depending on the target color sensitive material. ．． Mold inhibitors (eg, sodium benzoate), pH buffering agents, and the like may also be included.

In performing photographic processing according to the present invention, all processing temperatures may be appropriately set within the range of about 20 to 70°C, preferably in the range of 25 to 60°C.

As the fixer, one having a commonly used composition can be used. As a fixing agent, thiosulfates, thiocyanates, thioureas, thioglycols, water-soluble organic diols containing sulfur and oxygen in the molecule (for example, 3,
6-dithia-1,8-octyldiol) and the like. In addition to the fixing agent, the fixing solution contains stabilizers such as sulfites (e.g., sodium sulfite) (especially preferred when thiosulfate is used as the fixing agent), pH buffering salts, etc. Swell-inhibiting salts (eg, hardeners such as potash alum) may be included. In addition, the black and white developer used in silver dye bleaching and reversal color photography can contain commonly used developing agents.

As developing agents, dihydroxybenzenes (e.g. hydroquinone, hydroquinone sodium monosulfonate), 3-pyrazolidones (e.g. 1-phenyl-3
-pyrazolidones), aminophenols (e.g. N-
(methyl-p-aminophenol), ascorbic acid, etc. can be used alone or in combination.
The developing solution generally contains preservatives, alkaline agents, PH buffering agents, antifoggants, etc., and further contains solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, water softeners, etc. as necessary. , hardeners, tackifiers, etc. (the details of these additives are well known in the art).
. As explained above in detail, there are no particular limitations on the method for producing the silver halide emulsion of the light-sensitive material used in the present invention, the layer structure, photographic additives, photographic materials, photographic processing liquid, etc. By applying the bleaching method of the present invention, the following advantages can be obtained.

(1) Environmental pollution is negligible.

(a) If the bleaching solution is left for about a day after use, its oxidizing power will be almost gone, and it will not contain any compounds that cause environmental pollution.

(b) Bleach solution is almost neutral and does not require pH adjustment when disposed of.

(c) The bleaching solution is almost colorless and does not cause environmental pollution due to coloring even if it is discarded (conventional bleaching solutions are brown in color because they contain iron ions.

) (2) Liquid management can be done directly.

Activation and stopping of electrolysis can be easily and automatically achieved through control using at least one of a PH meter and a potentiometer.

(3) Sufficient color density can be obtained.

When conventional bleaching agents (e.g., Fe-EDTA complexes) are used, the reaction product between the oxidized color developer and the coupler is not sufficiently oxidized to the dye state and remains in the leuco state, resulting in only a low color density. However, in this method, the oxidizing power is moderately strong and sufficient color density can be obtained.

(4) It is inexpensive.

All the reagents used in the bleaching solution are inexpensive, and the electrolytic device has a simple configuration, is sufficiently effective, and is inexpensive.

(5) Bleaching is rapid.

A bleaching rate equivalent to that of known bleaching solutions (for example, bleaching solutions in which the bleaching agent is a complex salt of an aminopolycarboxylic acid and ferric iron, a ferric salt, or a ferrician iron salt) can be obtained.

Examples will be shown below to provide a more specific explanation of the present invention.

Example 1 A color reversal photographic material was prepared by coating each layer on a triacetate film support in the following order.

1st layer (red-sensitive emulsion layer) Coating solution: Red-sensitive silver iodobromide emulsion (silver iodide: 1-hydroxy-4-chloro-2-n-dodecylnaphthamide as J ■■ color, dibutyl phthalate as coupler solvent ) are mixed so that the silver/coupler molar ratio is 8.0.

Coated silver amount: 1.59Ag/M2.

Second layer (intermediate layer) A gelatin intermediate layer containing di-t-amyl hydroquinone dispersed therein.

3rd layer (green-sensitive emulsion layer) Coating solution: green-sensitive silver iodobromide emulsion (silver iodide: 6 mol (f
:, ) and magenta coupler emulsion (1-(2,4,6-trichlorophenyl)-3-[ as magenta coupler)
3-(2,4-t-amylphenoxyacetamide)
Benzamide]-5-pyrazolone and tricresyl phosphate as a coupler solvent are mixed such that the silver/coupler molar ratio is 9.5.

Coated silver amount: 1.5f! Ag/M2.

4th layer (yellow filter layer) A single layer of filter consisting of yellow colloidal silver and gelatin.

5th layer (blue-sensitive emulsion layer) Coating solution: Blue-sensitive silver iodobromide emulsion (silver iodide: 6 mol%)
, yellow coupler emulsion (α as yellow coupler)
-pivaloyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butanamide]acetanilide and dibutyl phthalate as the coupler solvent are mixed so that the silver/coupler molar ratio is 8.0. do.

Coated silver amount: 1.89Ag/M2. 6th layer (protective layer) A protective layer mainly made of gelatin.

After exposing a portion of this color photographic film to l/100 seconds through a light wedge using a tungsten lamp as a light source,
Inversion processing was performed using a known method as described below.

On the other hand, the remaining part of the color photographic film was exposed to light through a light wedge in the same manner as described above, and then processed according to the present invention.

The process and each liquid composition are as follows. Processing B (present invention) Processing process Assume that everything is the same as processing A.

Composition of each processing solution Everything is the same as Treatment A except for the bleach solution composition.

The above bleaching solution is placed in a cine strips type automatic processor tank (volume 151), and a carbon plate is inserted into the tank as an anode and a stainless steel plate is inserted as a cathode.

At this time, each electrode and the electrical conductor inside the tank (especially metal parts)
Avoid contact with. Effective electrode surface area at this time (
The value obtained by calculation) is about 20 d at both poles.

Both electrodes are installed parallel to the film surface, the anode is installed near the wall of the tank, and the cathode is installed inside the ring-shaped film without touching the film, and is fixed to the wall. Lead the terminal through the wall. The liquid is circulated by a pump. Next, direct current is applied to both poles from the power source to begin electrolysis. As for the electrolytic conditions, the current is 15A.
(The current density at both poles was about 0.75 A/d.) The voltage at this time was about 6. The solution before electrolysis has no bleaching ability at all. Quantity of electricity, voltage, ..., RedO associated with electrolysis time
Table 1 shows the x potential (vs. saturated calomel electrode), temperature, and amount of active bromine. The current efficiency for active bromine generation is approximately 78-1
00%.

Although the amount of active bromine did not increase in proportion to the electrolysis time,
The reason for this may be due to the cathodic reaction Br2+2e→2Br- or reaction with amines such as monoethanolamine.

The fact that the amount of active bromine does not increase in this way is advantageous for liquid management soils. Bleaching of the photosensitive material mentioned above starts after 30 minutes of electrolysis, and bleaching of the photosensitive material is completed in 2.5 minutes when electrolysis is performed for 60 minutes. Amount of silver remaining in the photosensitive material after processing for 4 minutes (2 locations: highest density area and lowest density area)
was determined by fluorescent X-ray analysis, and the results are shown in Table 2.

Also, the maximum density of the film processed in the same way is also the second value.
Shown in the table. B, G, and R indicate the maximum density measured through the blue, green, and red color separation filters, respectively. Table 2 shows that the amount of residual silver is almost the same as in Treatment A, indicating good results, and the maximum R density is slightly lower than in Treatment A, but this is not a major drawback.

Example 2 The same color reversal photographic material as in Example 1 was used, and after exposure, color reversal treatment was carried out by the following process C.

Processing C All treatment steps are the same as treatment A.

Composition of each processing solution Everything is the same as Treatment A except for the bleach solution composition.

Bleach solution (before electrolysis) The electrolysis method is the same as treatment B.

Regarding the electrolytic conditions, the current was 15A1 and the voltage at this time was about 6.

! 8!1. Similar to B, the bleaching prescription solution before electrolysis has no bleaching ability at all. The amount of electricity, voltage, and pH associated with electrolysis time.
．． RedOx potential (versus saturated calomel electrode), temperature, and amount of active bromine are shown in Table 3. The current efficiency of active bromine generation is about 76-100%.

Bleaching of the photosensitive material described above begins 30 minutes after the start of electrolysis, and bleaching of the photosensitive material is completed in 3 minutes at 60 minutes after the start of electrolysis.

The amount of silver remaining in the photosensitive material after processing for 4 minutes was determined and the results are shown in Table 4.

From Table 4, the amount of residual silver in Treatment C is almost the same as in Treatment A, indicating good results, and although the maximum density R is slightly lower than Treatment A, this is not a major drawback.

On the other hand, treatment C is slightly slower than treatment B in terms of bleaching speed, but the amount of decrease in dye density is small. Preferred embodiments of the invention are as follows.

1) The bleaching method according to claim 1 or 2, wherein the amino alcohol is a compound represented by general formula (1).

2) Bleaching treatment according to claim 1 or 2, in which the water-soluble compound that generates bromine by electrolytic oxidation is a water-soluble bromide; 3) The water-soluble compound that generates bromine by electrolytic oxidation is an alkali metal bromide salt or The bleaching method according to claim 1 or 2, wherein ammonium bromide is used.

4) Add amino alcohol to the bleaching solution at 1 x 10-
The bleaching method according to claim 1 or 2, wherein the bleaching treatment method contains 4 to 5 moles.

5) The bleaching process according to claim 1 or 2, in which the bleaching solution contains a PH buffer; 96) The bleaching process according to claim 1, in which electrolysis and photosensitive material processing are carried out in one tank.

7) A bleaching method as claimed in the claims, in which an electrolytic bath and a sensitive material processing bath are provided separately.

8) A bleaching method according to the claims, in which the pH of the bleaching solution is 6 to 8.5.

Claims (1)

[Scope of Claims] 1. A method of bleaching an exposed silver halide color photographic light-sensitive material using a bleaching solution after development, the bleaching solution comprising:
Bromine generated by electrolyzing an aqueous solution of a water-soluble bromine-containing compound that generates bromine through electrolytic oxidation and at least one type of amino alcohol coexist in an aqueous solution (may be in an electrolytic solution or a photosensitive material processing solution). 1. A method for bleaching color photographic materials, characterized by using a bleaching aqueous solution obtained by 2. A patent claim characterized in that the bleaching solution is a bleaching active aqueous solution obtained by electrolyzing an aqueous solution containing a water-soluble bromine-containing compound that generates bromine through electrolytic oxidation and at least one type of amino alcohol. The bleaching method according to item 1.