JP2640143B2 - Processing method of silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a method for washing and / or stabilizing water by washing water and / or a stabilizing solution with a reverse osmosis membrane. The present invention relates to a method for processing a silver halide photographic light-sensitive material which is purified by processing.

[Prior art] A silver halide photographic material is subjected to imagewise exposure,
Processing such as development, fixing, and washing with water are performed.

In recent years, from the viewpoints of environmental conservation and resource saving, reduction of harmful components in wastewater, reduction or no discharge of wastewater, and reduction of washing water have been required, and various studies have been conducted to meet these requirements. Have been.

Regarding the reuse of washing water, the ion exchange resin method (J. Ap
pl.Phot.Eng., 6, 120 (1980 ), the 5, 141 (1979)) and reverse osmosis unit (see USSR Patent No. 701963) are known.

Among these, improvements have been made in the technology of reverse osmosis membrane treatment of washing water, one of which is a color photographic processor,
A reverse osmotic pressure device is provided, and a liquid inlet, a concentration-side outlet, and a dilution-side outlet of the reverse osmotic pressure device are connected to the washing tank, the bleach-fixing tank, and the washing tank, respectively. The concentrated liquid produced by the reverse osmotic pressure treatment is returned to the bleach-fixing tank, and the diluting liquid is returned to the washing tank (JP-A-58-105150).

Further, after the silver halide color photographic light-sensitive material is color-developed, processed with a processing solution having a fixing ability, and then stabilized with a stabilizing solution without substantially washing with water, the stabilizing solution is subjected to reverse osmosis. A processing method for film processing has been proposed (Japanese Unexamined Patent Publication No.
According to this processing method, generation of yellow stain during long-term storage and stain immediately after processing is prevented.

Furthermore, after processing the silver halide color photographic light-sensitive material in a bath having a fixing ability so as to reduce the concentrated solution discharged from the reverse osmosis membrane processing apparatus and reduce the replenishment of the washing water,
When washing and / or stabilizing by the multi-stage countercurrent method, the overflow liquid from the washing tank and / or the stabilizing tank is introduced into the storage tank, and the liquid in the storage tank is subjected to reverse osmosis membrane treatment. There has been proposed a method for processing a silver halide color photographic light-sensitive material, in which a permeated liquid is processed in a washing tank and / or a stabilizing tank and a concentrated liquid is processed while returning the concentrated liquid to a storage tank (Japanese Patent Laid-Open No. Sho 62-25)
No. 4151).

The reverse osmosis membrane treatment method of the washing water and the stabilizing solution is a very useful method for greatly reducing the amount of water in the washing and stabilizing treatment steps. In addition, the stabilizing liquid is also called “stabilizing liquid”.

[Problems to be solved by the invention]

A problem in saving the washing water or the stabilizing solution is that, by bringing in from a bath having a fixing ability, the aminopolycarboxylic acid ferric complex salt in water or the solution in the washing tank or the stabilizing tank, for example, This is to increase the concentration of EDTA-Fe. In particular, when the concentration of the final bath exceeds 0.0003 mol /, an increase in yellow stain becomes a problem immediately after the treatment and during storage under high temperature and / or high humidity conditions. Also,
Since the silver concentration in the final bath increases, silver stains on the photosensitive material due to generation of silver sulfide and the like also occur.

All of the above-mentioned treatment methods are intended to purify the washing wastewater or the stabilized wastewater by reverse osmosis membrane treatment to obtain uncontaminated washing water or a stabilized liquid,
In the reverse osmosis membrane treatment, a reverse osmosis membrane which is highly treated so as to obtain high-purity washing water or a stabilizing solution has been used. In particular, in the processing apparatus of Japanese Patent Application Laid-Open No. 58-105150, valuable components in the washing water are collected and returned to the bleach-fixing tank, so that a reverse osmosis membrane that hardly allows solutes to pass through is used. I have. Such reverse osmosis membranes have micropores, which increase the operating pressure. In fact, the operating pressure in the processing apparatus of the JP 58-105150 is 40~50kg / cm ^2, and in the processing method of JP-60-241053 that the reverse osmosis membrane treatment the stabilizing solution Operating pressure is 55 kg / cm ² .

However, when the operating pressure is such high in the reverse osmosis membrane treatment, the liquid temperature rises due to the heat generated by the pump and adversely affects the treatment, so if this is to be cooled with cooling water,
There is a problem that the meaning of water saving is lost, and there is a disadvantage that when the operating pressure is increased, a large amount of power energy is required.

To avoid these drawbacks, it is necessary to reduce the operating pressure in reverse osmosis membrane treatment as much as possible. However, when the reverse osmosis membrane treatment is performed at low pressure, the rejection rate of the membrane, especially EDTA
The rejection of the aminopolycarboxylic acid ferric complex salt such as -Fe is likely to decrease. As described above, when water is saved in the washing water or the stabilizing solution using a reverse osmosis membrane treatment or the like, the concentration of EDTA-Fe in the washing water or the like increases, but the tendency is further enhanced by the low pressure. Is done. An increase in the concentration of EDTA-Fe causes the generation of yellow stain.

By the way, the present inventor has confirmed that EDTA-Fe deteriorates the reverse osmosis membrane while examining the influence of EDTA-Fe and the like. This is considered that the ferric iron of EDTA-Fe oxidizes and degrades the membrane, and the degradation degrades the efficiency of the reverse osmosis membrane treatment.

For this reason, it is desirable to prevent the membrane from being deteriorated by EDTA-Fe in the reverse osmosis membrane treatment.
The purpose of the present invention is to perform a reverse osmosis membrane treatment so that the reverse osmosis membrane is not deteriorated by EDTA-Fe.

[Means to solve the problem]

The present inventor has conducted various studies on the conditions under which the reverse osmosis membrane does not deteriorate, and found that the membrane does not deteriorate when a small amount of alkanolamine is present in the washing water or stabilizing solution for reverse osmosis membrane treatment. The present invention has been reached.

That is, the present invention provides a method for treating a silver halide photographic material in a bath containing a fixing ability containing an aminopolycarboxylic acid ferric complex salt, and then washing and / or stabilizing the alkanolamine in an amount of 0.0001 mol. The above object has been achieved by a method for processing a silver halide photographic light-sensitive material, characterized in that a washing water and / or a stabilizing solution containing at least the above-mentioned water are subjected to reverse osmosis membrane processing at an operating pressure of 10 kg / cm ² or less.

In addition, the present invention has its effect particularly when the reverse osmosis membrane treatment is performed at a low pressure of 10 kg / cm ² or less.

The effective content of alkanolamine in the washing water or stabilizing solution to be treated is 0.0001 mol / or more,
Preferably it is 0.0002 mol / or more, particularly preferably 0.0003 mol / mol.
Mol / or more. Alkanolamine is used to prevent oxidation by EDTA / Fe, etc., and its content is related to the content of the aminopolycarboxylic acid ferric complex salt in the washing water or the stabilizing solution. On the other hand, it is effective if the molar ratio is 1/30 or more, preferably 1/15 or more, particularly preferably 1/10 or more.

The alkanolamine may be added directly to the washing water or the stabilizing solution. The washing or stabilization is usually carried out by a multi-stage countercurrent system. In this case, the amount present in the final bath is preferably small, and is preferably 0.0001 mol / or less. This is because if the amount of the alkanolamine in the final bath is large, the adhesiveness of the surface of the photosensitive material dried out of the washing tank or the stabilizing tank is increased.

In the processing of the photosensitive material, the alkanolamine has a function of fixing, for example, a bleach-fixing bath, since bath components in the front tank have an effect of entering the bath of the rear tank as the photosensitive material moves. It may be added to a bath, a fixing bath, a bleaching bath, or a preceding developing bath. In particular, alkanolamine has properties as a preservative, and has a preserving effect of a developer, and thus is preferably added to a developing bath.

When the alkanolamine is added to the developing bath in this manner, the content of the alkanolamine in the developing solution is determined when the alkanolamine is brought into the bleach-fix solution or the like.
It is necessary that the molar ratio be at least 1/30 or more with respect to the amount of the aminopolycarbonic ferric complex salt, specifically, 0.01 to 0.3 mol /, preferably 0.02 to 0.2 mol /.
And particularly preferably in the range of 0.03 to 0.1 mol /.

When alkanolamine is added to the bleach-fix solution, the amount is 0.002 to 0.1 mol /, preferably 0.003 to 0.05 mol /, and particularly preferably 0.005 to 0.03 mol /.

As the alkanolamine, a compound represented by the following general formula [I] can be used.

General formula [I] Here, R ₁ , R ₂ and R ₃ represent an alkyl, aryl or alkenyl group. Each may have a substituent and may be condensed with an alkyl group or an alkenyl group.

However, at least one of R ₁ , R ₂ and R ₃ is an alkyl group having an OH group.

Specific examples of the alkanolamine are shown below, and triethanolamine and diethanolamine are particularly preferable.

I-1 NCH ₂ CH ₂ OH) ₃ I-2 H ₂ NCH ₂ CH ₂ OH I-3 HNCH ₂ CH ₂ OH) ₂ I-10 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ SO ₂ CH _{3 I-12 H 2 N-CCH} 2 OH) 2 Specific examples of the reverse osmosis membrane include, for example, DRA-40, DRA-80, and DRA-89 manufactured by Daicel Chemical Industries, Ltd., and in particular, DRA-80
Is preferred. Further, SU-200 and SU-700 manufactured by Toray Industries, Inc. can also be used.

As a material for these reverse osmosis membranes, it is preferable to use a polyacrylonitrile membrane, a polyvinylene carbonate membrane, or the like. Ethyl cellulose / polyacrylic acid film and cellulose acetate film can also be used.

As the structure of the reverse osmosis membrane, any of a spiral type, a tubular type, a hollow fiber type, a pleated type, and a rod type can be used. The film may be a single-layer film or a composite film, but a composite film made of a synthetic resin (synthetic composite film) is preferable from the viewpoint of durability against EDTA-Fe.

These reverse osmosis membranes include a permeated water membrane, a skin layer that governs membrane performance such as rejection, and a support layer that supports the skin layer. There are asymmetric membranes made of the same material and composite membranes made of different materials. Examples of asymmetric membranes are cellulose acetate membranes,
There is a polyamide membrane, and as a composite membrane, a polysulfone support layer coated with polyethyleneimine and tolylene diisocyanate to form a skin layer, or a furfrill alcohol polymerized to form a skin layer, etc. There is a synthetic composite membrane using a synthetic material, the details of which are described in the separate volume Chemical Industry 29-7 "Development and Practical Use of Advanced Separation Technology", pages 156 to 172, issued by Chemical Industry Co., Ltd. Synthetic composite membranes are preferably used in terms of rejection, permeated water, and durability against EDTA-Fe.

In the present invention, various compounds may be added to the washing water or the stabilizing solution. For example, a hardener represented by a magnesium salt or an aluminum salt, or a surfactant for preventing a drying load or unevenness, a tendency brightener for improving whiteness, a sulfite as a preservative, and the like. is there. Or LE West, Water Quality Criteria, Photographic Science and Engineering (Phot.Sci.a)
nd Eng.), Vol. 9, No. 6 (1965) and the like.

In the present invention, the stabilizing solution is a solution provided with an image stabilizing function that cannot be obtained by washing with water, and for this purpose, a component that achieves image stabilization is added in addition to the components added to the washing water. Things.

Examples of these components include, for example, a liquid to which formalin, bismuth salt, aqueous ammonia, ammonium salt and the like are added.

The pH of the washing water or the stabilizing solution in the present invention is usually around 7, but may be 3 to 9 due to the inflow from the previous bath. Also, the temperature of washing or stabilization is 5 to 40 ° C,
Preferably it is 10-35 degreeC. If necessary, a heater, a temperature controller, a circulating pump, a filter, a floating pig, a squeegee, and the like may be provided in the washing tank or the stabilizing tank.

The development processing of the photographic light-sensitive material of the present invention may be either processing for forming a silver image (black-and-white development processing) or development processing for forming a color image (color development processing). If an image is formed by the reversal method, a black-and-white negative development step is first performed, and then white exposure is performed or a color development processing is performed in a bath containing a fogging agent.

As the black-and-white developing process, a developing process, a fixing process, and a washing process are performed. When a stabilization process is performed after a development process, a stop process, or a fixing process, a water-wash process may be omitted. A development processing step using a lith developer as a developer may be performed.

The black-and-white developing solution used in the black-and-white developing process is used for generally known processing of a black-and-white photographic light-sensitive material, and can contain various additives generally added to the black-and-white developing solution.

Typical additives are developing agents such as 1-phenyl-3-virazolidone, metol and hydroquinone;
Preservatives such as sulfites, accelerators composed of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate, and inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole ,
Hard water softeners such as polyphosphoric acid, surface overdevelopment inhibitors comprising a small amount of iodide and mercapto compounds, and the like can be given.

The color developing process includes a color developing process, a bleaching process, a fixing process, a rinsing process, and a stabilizing process if necessary.The process includes a bleaching solution and a fixing solution. Alternatively, the bleach-fixing process can be performed using a single-bath bleach-fix solution, or a monobath process using a single-bath-developed bleach-fix solution capable of performing color development, bleaching, and fixing in a single bath. A step can also be performed.

A pre-hardening treatment step, a neutralization step thereof, a stop fixing treatment step, a post-hardening treatment step and the like may be performed in combination with these treatment steps.

Typical processing steps of the color development processing in the present invention are shown below, but the present invention is not limited thereto.

A. Color development-bleach-fix-wash-dry B. Color-development-bleach-fix-wash-stabilize-dry C. Color-development-wash-bleach-fix-wash-dry D. Color development-bleach-fix-wash-stable E. Color development-Bleaching-Fixing-Rinse-D. F. Color development-Rinse-Bleaching-Fixing-Rinse-Dry G. Color development-Bleaching-Bleach-fix-Rinse-Stabilize-Dry H. Color development- Bleach-Bleach-fix-Wash-Dry I. Color development-Bleach-Bleach-fix-Fix-Wash-Stabilize-Dry J. Color development-Bleach-Bleach-fix-Fix-Wash-Dry When the previous step is a water washing step, the water washing step can be omitted and the step immediately after the water washing can be used as a stabilization step.

The color developing solution that can be used in the present invention is an alkaline aqueous solution mainly containing an aromatic primary sphere amine color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used. Representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N, N-diethylaniline. Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. These compounds can be used in combination of two or more depending on the purpose.

In addition, various preservatives are used in the color developer, but in order to cover the decrease in color developability caused by removing benzyl alcohol, the competitive reactivity to the coupling reaction between the color developer oxide and the coupler is increased. Small,
Further, it is preferable that the developing activity is small with respect to silver halide.

From such a viewpoint, it is preferable to keep the sulfites and hydroxylamine, which have been widely used in the past, as small as possible, and it is particularly preferable not to use them at all.

Such sulfites, hydroxylamine derivatives such as hydroxylamine substituted with alkyl instead of hydroxylamine, hydroxamic acids, hydrazines, hydrazinos, phenols, α-hydroxyketones, α-
Aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds,
It is preferable to use an organic preservative such as a condensed amine.

These are disclosed in Japanese Patent Application No. 61-147823 and JP-A-63-30845.
No. 63-21647, No. 63-44655, Japanese Patent Application No. 61-197760
No., JP-A-63-43140, Japanese Patent Application No. 61-198987, and 61-2
No. 01861, JP-A-63-43138, European Patent Publication 254280,
JP-A-63-44657, JP-A-63-446565, U.S. Pat.
No. 5,503, No. 2,494,903, JP-A-52-143020, Tokubo Akira
No. 48-30496.

It is desirable to add the above preservative to the color developing solution so as to have a concentration of 0.005 mol /, preferably 0.03 mol / to 0.1 mol /.

The color developing solution used in the present invention is preferably pH 9-1.
1, more preferably 9.5 to 10.5, and the color developing solution may contain other known developing solution components.

In order to maintain the above pH, it is preferable to use various buffers. As circulating agents, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, calcium borate,
Sodium tetraborate (borax), potassium tetraborate, o
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer to be added to the color developer is preferably 0.1 mol / or more, and particularly preferably 0.1 mol / to 0.4 mol /.

In addition, various chelating agents can be used as a calcium or magnesium precipitation inhibitor during color development or to improve the stability of the color developing agent.

Specific examples of the chelating agent are shown below, but are not limited thereto.

・ Nitrilotriacetic acid ・ Diethylenetriaminepentaacetic acid ・ Ethylenediaminetetraacetic acid ・ Triethylenetetraminehexaacetic acid ・ N, N, N-trimethylenephosphonic acid ・ Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid ・ 1,3 -Diamino-2-propanoltetraacetic acid. Transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2 , 4-Tricarboxylic acid 1-hydroxyethylidene-1,1-diphosphonic acid N, N'-bis (2-hydroxybenzyl) ethylenediamine-N-N'-diacetic acid These may be used in combination.

The amount of these sylating agents to be added may be an amount sufficient to block metal ions in the color developing solution. For example, 1
It is about 0.1g to 10g per unit. Further, an optional development accelerator can be added to the color developer if necessary.

As development accelerators, JP-B-37-16088 and JP-B-37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-9919, and thioether compounds represented by U.S. Pat. p-phenylenediamine compound, JP-A-50-1377
No. 26, JP-B-44-30074, JP-A-56-156826 and 5
Quaternary ammonium salts represented by 2-43429, etc .; p-aminophenols described in U.S. Pat. Nos. 2,610,122 and 4,119,462;
Nos. 4,230,796 and 3,253,919, JP-B-41-11431
Nos. 2,482,546, 2,596,926 and 3,582
Amine compounds described in 2,346, etc., JP-B-37-16088
No. 42-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41
-11431, 42-23883 and U.S. Pat.
Phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

In the present invention, an optional antifoggant can be added as required. As antifoggants, alkali metal halides such as potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
Representative examples include nitrogen-containing heterocyclic compounds such as 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developing solution used in the present invention preferably contains a fluorescent whitening agent. As the fluorescent whitening agent, a 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The amount added is 0.5 g / preferably 0.1-4 g /.

Further, various surfactants such as alkylsulfonic acid, arylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as needed.

The addition temperature of the color developing solution of the present invention is 20 to 50 ° C, preferably 30 to 40 ° C.

The bleaching solution or bleach-fixing solution used in the present invention contains an iron complex as a bleaching solution. Of the iron complexes, aminopolycarboxylate iron complexes are preferred, and the amount added is 0.01 to
1.0 mol / preferably 0.05 to 0.50 mol /. Also,
The fixing agent in the fixing solution or the bleach-fixing solution includes thiosulfate. In particular, ammonium thiosulfate is preferable, and the amount of addition is 0.1 to 5.0 mol /, preferably 0.5 to 2.0 mol.
mol /. As a preservative, addition of levosulfate is generally used. In addition, ascorbic acid, an adduct of carbonyl bisulfate, or a carbonyl compound may be added. Further, a buffer, a fluorescent whitening agent, a chelating agent, a fungicide, and the like may be added as necessary.

Various compounds can be used as a bleaching accelerator in the bleaching solution and / or the prebath thereof. For example, U.S. Pat.No. 3,893,858, German Patent 1,2
No. 90,812, JP-A-53-95630, compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129 (July, 1978), and thiazolidine described in JP-A-50-140129. Derivatives, thiourea derivatives described in U.S. Pat.No. 3,706,561,
Iodides described in JP-A-58-16235, German Patent No.
Polyethylene oxides described in 2,748,430 and polyamine compounds described in JP-B-45-8836 can be used.

As the photographic light-sensitive material according to the present invention, ordinary black-and-white silver halide photographic light-sensitive materials (for example, black-and-white light-sensitive materials for photography, X-
black-and-white light-sensitive material for ray, black-and-white light-sensitive material for printing, etc.), ordinary multilayer color light-sensitive material (for example, color negative film, color reversal film, color positive film,
A color negative film for a movie, etc.) and a sensitized material for infrared light for a laser scanner.

The silver halide emulsion layer of the photographic light-sensitive material of the present invention, the type of silver halide used for the surface protective layer, etc., production method, chemical sensitization method, antifoggant, stabilizer, hardener, antistatic agent,
There are no particular restrictions on couplers, plasticizers, lubricants, coating aids, matting agents, brighteners, spectral sensitizers, dyes, ultraviolet absorbers, supports, etc., for example, Product Licensing 92. Volume 107-110 (1971 December 12)
Mon) and Research Disclosure Magazine (Research D)
isclosure) No.17643 (December 1978)
(November 1991), the same magazine, No.23815 (February 1984).

As the process of the present invention, a color developing process having a color developing step is preferable because the effects of the present invention can be effectively exhibited.

Accordingly, as a light-sensitive material suitable for the processing of the present invention, a silver halide color photographic light-sensitive material can be mentioned. In particular, a so-called high silver chloride emulsion having a high silver chloride content is preferably used.
Light-sensitive materials for color paper are suitable. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%,
95 mol% or more is more preferable. For the purpose of reducing the replenishment amount of the developing solution, an emulsion of substantially pure silver chloride having a silver chloride content of 98 to 99.9 mol% is also preferably used.

The coupler preferably used in the color light-sensitive material of the present invention will be described below.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,401,7
No. 52, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020 and 1,476,760, U.S. Pat.No. 3,973,96
No. 8, No. 4,314,023, No. 4,511,649, European Patent No. 2
No. 49,473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
Nos. 619 and 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,064, Research Disclosure No. 24220 (June 1984), JP-A-60-3355
No. 2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-35
No. 730, No. 51-118034, No. 60-185951, U.S. Pat.
No. 4,500,630, No. 4,540,654, No. 4,556,630, WO
(PCT) 88/04795 and the like are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,9292, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453
A, U.S. Pat.Nos. 3,446,622, 4,333,999,
No. 4,753,871, No. 4,451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212, No. 4,296,199,
Preferred are those described in JP-A-61-42658.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No. 17643 VII.
Section G, U.S. Pat.No. 4,163,670, JP-B-57-39413,
U.S. Pat.Nos. 4,004,929 and 4,138,258; British Patent No.
Those described in 1,146,368 are preferred. It is also preferable to use a coupler described in U.S. Pat. No. 4,774,181 that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,215,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, British Patent 2,10
No. 2,173.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD17643, VII-F above.
Patents, JP-A-57-151944 and JP-A-57-1542
No. 34, No. 60-184248, No. 63-37346, U.S. Pat.
Those described in 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
Preferred are those described in JP-A-31-188, JP-A Nos. 59-157638 and 59-17840.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618 and the like, multi-equivalent couplers described in
185950, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR described in JP-A-62-24252 and the like.
Coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after release as described in EP 173,302A, RD No. 1144
9, 24241, bleach accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat.No. 4,553,477, etc., and leuco dyes described in JP-A-63-75747 are released. Couplers and couplers that release a fluorescent dye described in U.S. Pat. No. 4,774,181 are exemplified.

(Operation)

In the present invention, when an alkanolamine is present in the washing water or the stabilizing solution when the washing water or the stabilizing solution is used and then subjected to the reverse osmosis membrane treatment, deterioration of the reverse osmosis membrane is prevented. Its mechanism of action is unclear,
It is thought that ferric iron of the polyaminocarboxylic acid ferric complex salt oxidizes and deteriorates the reverse osmosis membrane, but it has not been experimentally confirmed exactly. Further, the mechanism of the effect is not clear, and alkanolamine itself has an action of blocking iron ions, but polyaminocarboxylic acid also has a function of blocking iron ions, and polyaminocarboxylic acid Since the ferric complex salt itself is in a form in which iron ions are blocked, it is not possible to explain the action of the alkanolamine only by its properties.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to examples. However, the present invention is not limited to only these examples.

Example 1 A color photographic paper described below, which was cut to a width of 117 mm, was exposed with an automatic printer, and had a washing tank with a reverse osmosis membrane module attached thereto. Based on the processing conditions shown in Table 1 under the following processing conditions, the steel sheets were treated at 60 m / day for 20 days. The operation time of the reverse osmosis treatment device per day was 16 hours per day.

In FIG. 1, 1 is a color developing tank (D), 2 is a bleach-fixing tank (BF), 3, 4 and 5 are a first washing tank W ₁ and a second tank 2, respectively.
A washing tank W ₂ and a third washing tank W ₃ , and new washing water 6 is supplied to a final third washing tank (W ₃ ) 5, and the washing water in the same tank is supplied to the second washing tank (W ₂ ) in the preceding stage. 4 is sent to the first washing tank (W ₁ ) 3 via the path 8 and then to the first washing tank (W ₁ ) 3 via the path 8.

Rinse water is taken out from the second rinsing tank (W ₂ ) 4 by the path 10, and the reverse osmosis membrane module (RO) 12 is supplied by the pump (P) 11.
Send to The operation was performed under the conditions of a liquid sending pressure of 4 kg / cm ² and a water sending flow rate of 2 / min. The permeated water was supplied to the third washing tank (W ₃ ) 5 through the path 13, and the concentrated liquid was sent to the second washing tank (W ₃ ) through the path 14. ₂ ) Returned to 4. Reverse osmosis membrane in reverse osmosis membrane module (RO) 12
Uses a spiral RO module element DRA-80 (effective membrane area 1.1 m ² , polysulfone-based composite membrane) manufactured by Daicel Chemical Co., Ltd.
I mounted it on PV-0321.

The color developing tank (D) 1 and the bleach-fix tank (B)
F) The 2 and first to third rinsing tank (W ₁ ~W ₃₎ 3~5, was supplied color developing solution described later described, the bleach-fixing solution and washing water.
Reverse osmosis membrane module (RO) during color photographic paper processing time
Ran continuously.

The processing steps in this processing apparatus are as shown in Table 1.

The treatment liquid formulation used is as follows.

Color developer Rinse solution (mother liquor, replenisher) Tap water (calcium 23 mg / magnesium 3 mg / contained, conductivity 170 μs / cm) The printing paper was run under the above conditions. Also, when the content of triethanolamine in the color developing solution was changed, and when diethanolamine was used in place of the triethanolamine, a running process was also performed. For comparison, the color developing solution, the bleach-fix solution, and the washing water were used. The running treatment was also performed in the case where no alkanolamine was contained. The condition of the running process is 3rd
It is shown in the table.

Table 4 shows the concentration of EDTA-Fe in the reverse osmosis permeate at the time of the 20-day treatment as Fe. In addition, a white background portion of the photographic paper after the processing after the processing for 20 days was collected, and was taken at 80 ° C and 70 ° C.
% For 3 days, and the increase in yellow stain during this period was examined.

In Run-1, when the reverse osmosis membrane was replaced with a new one after the treatment for 20 days, the Fe content was 1.8 mg / and the removal rate was 9%.
It was 9.4%.

As a result of examining the adhesiveness of the color photographic paper treated on the 20th day by the method described below, the results are as shown in Table 5.

Adhesiveness: photographic paper (3.5cm x 3.5cm) treated after total exposure, 25
℃, relative humidity 80%, leave for 2 days, superimpose the emulsion surface, apply a load of 500g, further 35 ℃, relative humidity
It was left for 3 days in an environment of 80%. Thereafter, the superposition was separated and the surface was observed.

Multilayer color photographic paper A multilayer color photographic paper having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution is prepared by mixing and dissolving an emulsion, various chemicals, and an emulsified dispersion of a coupler. The preparation methods are described below.

Preparation of coupler emulsion 19.1 g of yellow coupler (ExY)
27.2cc of ethyl acetate per 14.4g of color image stabilizer (Cpd-1)
And 7.7 cc of a solvent (Solv-1) were added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.

Thereafter, each emulsion for magenta, cyan and intermediate layers was prepared in the same manner. The compounds used for each emulsion are shown below.

(Cpd-5) Mixing inhibitor: same as Cpd-2, provided that R = C ₈ H ₁₇ (t) (Cpd-6) Color image stabilizer 6a: 6b: 6c = 5: 8: 9 mixture (weight) ratio) (UV-1) UV absorber Cpd-6a: 6b: 6c = 2: 9; 8 mixture (weight ratio) (Solv-2) Solvent 0 = P0-C ₈ H ₁₇ (iso)) ₃ (Solv-3) Solvent 0 = P0-C ₉ H ₁₉ (iso)) ₃ The following dyes were added to the emulsion layer to prevent irradiation.

Same as Green-sensitive layer Dye-R. However, n = 1.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Next, the emulsion used in this example will be described.

Blue-sensitive emulsion; average particle size 1.1 μm, coefficient of variation (standard deviation divided by average particle size = s / d) 0.1 according to a conventional method
A monodisperse cubic silver chloride emulsion (containing K ₂ IrCl ₆ , 1,3-dimethylimidazoline-2-thione) was prepared.
A 0.6% solution of the spectral sensitizing dye for blue (S-1) was added to 1.0 kg of 26 kg.
cc and further a silver bromide fine grain emulsion of 0.05 μm was added at a ratio of 0.5 mol% to the host silver chloride emulsion. After ripening, sodium thiosulfate was added to perform optimal chemical sensitization to obtain a stabilizer (Stb-1). ) Was added by adding 10 ^-4 mol / mol Ag.

Green-sensitive emulsion; silver chloride particles containing K ₂ IrCl ₆ and 1,3-dimethylimidazoline-2-thione were prepared by a conventional method, and then 4 × 10 ^-4 mol / mol Ag sensitizing dye (S-2) And KB
After ripening and ripening, sodium thiosulfate was added for optimal chemical sensitization, and a stable solution (Stb-1) was added at 5 × 10 ⁻⁴ mol / mol Ag to give an average particle size of 0.48 μm and a variation coefficient of 0.10 μm.
Was prepared.

Red-sensitive emulsion: prepared in the same manner as the green-sensitive emulsion. However, S-
In place of 2, a sensitizing dye (S-3) was used in an amount of 1.5 × 10 ⁻⁴ mol / mol Ag.

 Next, the compounds used are shown.

(Layer Structure) The composition of each layer in the sample is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support: polyethylene laminated paper [polyethylene on the first layer side contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue sensitive layer) Silver halide emulsion 0.30 gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Second layer (color mixture preventing layer) Gelatin 0.99 Color mixture inhibitor (Cpd-2) 0.08 Third layer (green sensitive layer) Silver halide emulsion 0.36 Gelatin 1.24 Magenta coupler (ExM1) 0.31 Color image stabilizer (Cpd-3) 0.25 Color image stabilizer (Cpd-4) 0.12 Solvent (Solv-2) 0.42 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV -1) 0.62 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-3) 0.24 Fifth layer (red sensitive layer) Silver halide emulsion 0.23 Gelatin 1.34 Cyan coupler (ExC1, C2, C3 1: 2: 2 blend ) 0.34 Color image stabilizer (Cpd-6) 0.17 Polymer (Cpd-7) 0.40 Solvent (Solv) 4) 0.23 Sixth Layer (ultraviolet absorbing layer) Gelatin 0.53 UV absorber (UV-1) 0.21 solvent (Solv-3) 0.08 Seventh Layer (protective layer) Gelatin 1.33 Polyvinyl acrylic modified copolymer of an alcohol (modification degree
17%) 0.17 Liquid paraffin 0.03 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a hardening agent for each layer.

 A color photographic paper was prepared as described above.

Example 2 The processing conditions and the processing liquid were the same as those in Example 1, except that the washing tank of the processing apparatus was of a four-stage countercurrent type, and the running conditions shown in Table 3 were changed to the running conditions shown in Table 6 below. The color photographic paper was processed in the same manner as in Example 1.

Table 7 shows the concentration of EDTA-Fe in the reverse osmosis permeate at the time of the 20-day treatment as Fe. Table 7 also shows the results of examining the adhesiveness of the color photographic paper after the 20-day treatment by the method described in the examples. After the processing for 20 days, collect the white part of the photographic paper after the processing, and under the condition of 100 ° C (no humidity adjustment)
Was stored for 1 day, and the increase in yellow stain during this period was examined.

After the treatment in Run-1 for 20 days, the reverse osmosis membrane was replaced with a new one, and the Fe removal rate was 99.3%.

〔The invention's effect〕

According to the present invention, in a method for processing a silver halide color photographic light-sensitive material, reverse osmosis is carried out in a state containing alkanolamine in washing water and / or a stabilizing solution,
Reverse osmosis membrane does not deteriorate during reverse osmosis membrane treatment,
Reverse osmosis membrane treatment is performed efficiently. And the removal rate of the polyaminocarboxylic acid ferric complex in the reverse osmosis membrane treatment is kept high.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a processing apparatus used in an embodiment of the present invention. 1 ...... color development tank D, 2 ...... bleach-fixing tank BF 3 ...... first washing tank W _1, 4 ...... second washing tank W ₂ 5 ...... third washing tank W _3, 6 ...... new washing water 9 ... drainage, 10 ... route 11 ... liquid pump P, 12 ... reverse osmosis tank RO 13 ... route, 14 ... route

Claims (1)

(57) [Claims] 1. A processing method comprising treating a silver halide photographic light-sensitive material in a bath having a fixing ability containing an aminopolycarboxylic acid ferric complex salt, followed by washing and / or stabilization.
A method for processing a silver halide photographic light-sensitive material, comprising subjecting a washing water and / or a stabilizing solution containing at least 0.0001 mol / alkanolamine to reverse osmosis membrane treatment at an operating pressure of 10 kg / cm ² or less.