JPS62254151A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To considerably reduce the amount of water used for washing and/or stabilization by introducing a liq. overflowing a washing tank and/or a stabilization tank into a storage tank, subjecting the liq. in the storage tank to reverse osmosis and returning a liq. passed through a reverse osmosis membrane to the washing tank and/or the stabilization tank and a concd. liq. to the storage tank. CONSTITUTION:A concd. liq. D not passed through a reverse osmosis membrane F is returned to a storage tank B. The concd. liq. D separated by reverse osmosis is returned to the tank B, mixed with a liq. A overflowing a washing or stabilization tank and subjected to reverse osmosis. Since the separated concd. liq. D is returned to the tank B, this method is considered to be unreasonable. The concn. of the concd. liq. D is, however, gradually increased by repeatedly carrying out the stages and finally the amount of the concd. liq. D can be considerably reduced as compared with the amount of a passed liq. C even in case of a small-sized reverse osmosis unit E. Accordingly, the amount of washing water or a stabilizing soln. fed newly to the washing or stabilization tank can be considerably reduced.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a processing method for silver halide color photographic light-sensitive materials, and in particular to a processing method that can significantly reduce the amount of water used in washing and/or stabilization processing steps. It is something.

(Prior art) Conventionally, the processing process of silver halide photographic materials includes a water washing process, but in recent years, due to environmental conservation water resource and cost issues, it has been suggested that the amount of water used should be reduced. It's here. For example, the Journal of the Society of
Motion Picture and Television Engineers (Journal of the 5ocie)
ty of Motion Picture and T
e1evision Engineers) Volume 64,
“Water Flow Lake in Immersion Washing” on pages 248-253 (May 1955 issue)
of motion picture film (Water)
Flow Rates in Immersion-
Washing of Motion Picture
Film 'Nis R Goldwasser (S, R
, Goldwasser) proposes a method of reducing the amount of washing water by making the washing tank multistage and causing the water to flow countercurrently. This method is adopted in various automatic processors as an effective means for saving water.

According to this multi-stage countercurrent system, the amount of water supplied can be reduced as the number of washing tanks increases, but an increase in the number of washing tanks has the disadvantage of increasing the installation area of the automatic developing machine.

In addition, by processing this multistage countercurrent water washing method with a multistage countercurrent stabilizing bath that has an image stabilization function,
A method for stabilizing images and saving water was published in Japanese Patent Application Laid-open No. 57-8.
It is described in Publication No. 543.

However, even if such a stabilizing bath is used, it has the same disadvantage that the number of baths must be increased in order to further save water.

Therefore, the number of washing or stabilizing tanks in the multistage countercurrent system is 2 to 6, and in most cases, 2 to 4 tanks are used.

Therefore, the water saving effect does not necessarily satisfy the requirements in this industry.

Extensive water conservation without increasing the number of washing or stabilizing tanks will increase the concentration of fixing or bleach-fixing components during washing, causing yellow stain on the processed photographic material.
The stability of the dye image may deteriorate. Therefore, there is a strong demand for further water saving within a realistic installation area without impairing the properties of the photosensitive material after processing.

In response to such demands, methods using reverse osmosis treatment equipment are disclosed in Japanese Patent Application Laid-open Nos. 58-105150 and 60-24105.
It is described in Publication No. 3.

In both of these methods, the overflow liquid from the washing tank or stabilization tank is directly connected to the reverse osmosis treatment equipment, the permeated liquid coming out of the reverse osmosis treatment equipment is supplied to the washing or stabilization tank, and the concentrated liquid is reversed again. It can be introduced directly into a bleach-fixing bath or silver recovery equipment without any penetration treatment. However, when this method is actually carried out, unless it is a large device with a large reverse osmosis membrane area and a pump that can load high pressure, the clean liquid that has passed through the reverse osmosis membrane (hereinafter referred to as permeate) is It is very difficult to sufficiently reduce the amount of concentrated liquid (hereinafter referred to as concentrated liquid) that is discharged without passing through the reverse osmosis membrane, compared to the amount of concentrated liquid (hereinafter referred to as concentrated liquid).

In other words, the amount of concentrated liquid discharged outside the system is greater than the amount of permeate fed to the washing or stabilization tank, and unless liquid is newly supplied to the washing or stabilization tank, washing or stabilization will not be possible. The amount of liquid in the stabilization tank decreases rapidly, and it becomes impossible to process the liquid.

In order to prevent this, it is necessary to newly supply the same amount of liquid as the amount of concentrated liquid discharged to the washing or stabilization tank, and as a result, the purpose of saving water cannot be fully achieved. Of course, as described above, if a large-sized device is used, it is possible to reduce the amount of concentrated liquid compared to the amount of permeated liquid, but this requires a large amount of equipment cost.

On the other hand, since reverse osmosis membranes are extremely fine filtration membranes, they are subject to various factors such as calcium and magnesium in the liquid, deposits of silver salts eluted from silver halide color photographic materials, and bacteria. This has the disadvantage that it becomes clogged due to the proliferation of water, and the amount of permeate decreases, making it impossible to achieve the purpose of water conservation.

(Objective of the Invention) The first object of the present invention is to provide a silver halide color photographic material that can greatly reduce the amount of water used for washing and/or stabilization.
The object of the present invention is to provide a method for processing color photosensitive materials (hereinafter simply referred to as color photosensitive materials).

A second object of the present invention is to provide a method for processing color photosensitive materials that can greatly reduce the amount of water used for washing and/or stabilization using a small-sized reverse osmosis processing apparatus.

A third object of the present invention is to provide a method for processing color photosensitive materials using a reverse osmosis processing apparatus that prevents clogging of the reverse osmosis membrane and provides stable processing performance over a long period of time.

Furthermore, the fourth object of the present invention is to reduce the consumption of processing agents,
The object of the present invention is to provide a method for processing color photosensitive materials that contributes to cost reduction and environmental conservation.

(Means for Solving the Problem) The above object of the present invention is to introduce the overflow liquid from the washing tank and/or stabilization tank once into the storage tank when performing water washing and/or stabilization using a multi-stage countercurrent method. This was achieved by subjecting the liquid in the storage tank to reverse osmosis treatment, and processing the permeate from the reverse osmosis treatment device into a washing and/or stabilization tank, while returning the concentrated liquid to the storage tank. .

In the present invention, an overflow liquid means a liquid that overflows from a washing or stabilizing tank as a result of the liquid being supplied to the washing or stabilizing tank. Further, as described above, the permeated liquid refers to the liquid that has passed through the reverse osmosis membrane, and the concentrated liquid refers to the liquid that comes out of the reverse osmosis device without passing through the reverse osmosis membrane.

In the present invention, washing with water is a process for ensuring post-processing performance by washing out processing liquid components that have adhered to or occluded in the color photosensitive material, as well as photosensitive material constituents that are no longer needed during the processing process. .

Therefore, if the effect of the process is entirely attributable to the washing out, it corresponds to the water washing of the present invention, regardless of the amount of water used or the composition.

Furthermore, in the present invention, stabilization is a process that can impart properties to the processed color photosensitive material that cannot be obtained by washing with water as described above.

The present invention is disclosed in Japanese Unexamined Patent Publication No. 58-105150, No. 6°-24
Unlike the method described in No. 1053, in which the concentrated liquid is supplied as it is to a silver recovery device or a bath having fixing ability, the method is characterized in that the concentrated liquid is once returned to the storage tank and subjected to repeated reverse osmosis treatment. An example of the present invention is shown in FIG.

In Figure 1, L2 is a color developing tank, L2 is a bleach-fixing tank,
Tt is the first washing tank, Tt is the second washing tank, T3 is the third washing tank, A is the overflow liquid of the first washing tank, B is the storage tank,
E is a reverse osmosis treatment device, F is a reverse osmosis membrane, and P is a liquid pump. C is permeated water that has passed through the reverse osmosis membrane F and been purified; G
is the supplementary rinsing water. The feature of the present invention described above is that the concentrated liquid that has not passed through the reverse osmosis membrane is returned to the original storage tank B.

H is a surplus liquid that is discharged outside the system due to the supply of the replenishment washing liquid G.

In the method of the present invention, the concentrated liquid separated by reverse osmosis treatment is returned to the storage tank and mixed with the overflow liquid from the water washing or stabilization tank. This may seem unreasonable since the concentrated liquid that has been drained would be returned again.

However, by repeating this process, the concentration of the concentrate gradually increases, and the final result is that even in a small reverse osmosis treatment device, the amount of concentrate can be significantly reduced compared to the amount of permeate. This brings about the unexpected effect that the amount of washing water or stabilizing liquid newly supplied to the washing or stabilizing tank can be greatly reduced.

In addition, the present inventors added ethylenediaminetetraacetic acid, N-hydroxyethylenediaminetriacetic acid, 1,3-diaminopropanetetraacetic acid, and salts thereof, the following general formula (1), (If It has been found that clogging of reverse osmosis membranes can be solved by containing at least one selected from the benzotriazole derivatives shown in ) in the washing tank.

General formula (1) % formula % In the formula, R1, R2, R3, R4 and R5 are hydrogen atom, halogen atom (chlorine atom, fluorine atom, etc.), alkyl group, substituted alkyl group, hydroxyl group, amino group, nitro group , represents a carboxyl group or a sulfonic acid group, and may be the same or different. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and the substituted alkyl group preferably has 1 to 10 carbon atoms in total, and examples of substituents include halogen atoms, hydroxyl groups, amino group, sulfonic acid group, nitro group, carboxyl group, etc.

Rl"Rs is preferably a hydrogen atom, a halogen atom, a lower alkyl group, or a hydroxyl group, especially Rl-R
Preferably, all s are hydrogen atoms.

General Formula (H) In the formula, R& and R'l represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a nitrogen-containing heterocyclic group. Here, R6 and R7 may be the same or different.

The thylkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and the total number of carbon atoms in the substituted alkyl group is preferably 1.
~10. Examples of the substituent include a halogen atom, a hydroxyl group, an amino group, a sulfonic acid group, a nitro group, and a carboxyl group.

The aryl group represents a phenyl group or a naphthyl group. As a substituent of the substituted aryl group, a halogen atom,
Examples include an alkyl group, an amino group, a sulfonic acid group, a nitro group, and a carboxyl group. Further, the total number of carbon atoms in the aryl group or substituted aryl group is preferably 6.
-16, more preferably 6-10.

Examples of the nitrogen-containing heterocyclic group include a pyrazole group, an oxazole group, an isoxazole group, a thiazole group, an isothiazole group, a thiadiazole group, a pyridyl group, and a pyridazine group.

Further, it is preferable that the washing water or the stabilizing bath be water softened using an ion exchange resin or the like in order to prevent clogging of the membrane.

As a water softening method, a combination of a Na type strongly acidic cation exchange resin or an H type cation exchange resin and an OH type anion exchange resin can be used.

Furthermore, by introducing the liquid in the storage tank into a bath having fixing ability, the present inventors can reduce the amount of components contained in the replenisher to the bath and the amount of water used for preparing the replenisher, resulting in water conservation and It was discovered that the amount of waste liquid could be reduced even further.

Various methods can be adopted for introducing the liquid in the storage tank into the bath having fixing ability. For example, when the overflow liquid to be subjected to reverse osmosis treatment is obtained from a tank (first washing tank or first stabilization tank) immediately following a bath having fixing ability, the liquid in the storage tank is directly introduced into the bath having fixing ability. You can also
When obtaining overflow liquid from a tank following the first washing tank or first stabilization tank, the liquid in the storage tank is supplied to the front tank of the tank from which the overflow liquid was obtained, and the fixing ability is increased via these front tanks. It may also be introduced into a bath containing

As the reverse osmosis treatment equipment used in the present invention, any known equipment can be used without limitation, but the method of the present invention is particularly suitable for small-sized equipment in which the area of the reverse osmosis membrane is 3 m2 or less and the working pressure is 30 kg/m” or less. In particular, it is useful in ultra-small equipment of 2 m" or less and 20 kg/m" or less. That is, according to the present invention, it is useful in such small-sized, low-pressure reverse osmosis equipment. It is also possible to obtain sufficient water saving effects.

As the reverse osmosis membrane included in the reverse osmosis treatment apparatus used in the present invention, a cellulose acetate membrane, an ethyl cellulose/polyacrylic acid membrane, a polyacrylonitrile membrane, a polyvinylene carbonate membrane, etc. can be used.

Further, the liquid feeding pressure used is 5 to 60 kg/cn, but according to the present invention, a sufficient water saving effect can be obtained with a pressure of 30 kg/cd or less, and more preferably 20 kg/cn to reduce equipment cost, power consumption, noise, heat generation, etc. /cJ or less.

As the structure of the reverse osmosis membrane, any of a spiral type, a tuple type, a hollow fiber type, a pleated type, and a rondo type can be used.

Ethylenediaminetetraacetic acid used in the present invention, N
-Hydroxyethylethylenediaminetriacetic acid, 1.3-
As the salt of diaminopropane tetraacetic acid, sodium salt,
Potassium, ammonium and lithium salts are used. Particularly preferred are sodium salts and potassium salts.

Further, as the compounds represented by the general formulas (, I) and (II), the following are preferable.

I-31-6 0 ■ 1st + T-1 H-2 t-5 II-6 The compounds represented by the general formulas (I) and (II) of the present invention are known and commercially available. It is also easily available.

The amount of the above compound contained in the washing tank or stabilization tank is 0.01 to 5 g per liquid 1) in the washing tank or stabilization tank.
Preferably 0.1-3g, particularly preferably 0.3-3g
It is. In order to contain these in the washing or stabilizing tank, they can be added directly into the washing or stabilizing tank, or they can be added to the washing or stabilizing liquid that is replenished into the final washing or stabilizing tank. You can leave it there. It may also be added to permeated water from reverse osmosis treatment. Preferably, it is added to the washing or stabilizing liquid that is replenished into the final washing or stabilizing tank.

In the present invention, the liquid in the storage tank is a bath having fixing ability,
Specifically, it can be introduced into a fixing bath or a bleach-fixing bath. As a method of introduction, in addition to the above-mentioned method, it is also possible to use a method of using it as a preparation solution when preparing a replenisher solution for these baths.

The fixing bath and bleach-fixing bath to be introduced are preferably those used in the process preceding the washing or stabilization process targeted by the present invention, but may be used in other processes or in other automatic processors.

In addition to the above-mentioned ethylenediaminetetraacetic acid and the compound represented by general formula (1), a bactericide or an antifungal agent (anti-piping agent) may be used in combination with the washing water or stabilizing liquid of the present invention.

For example, JP-A-57-157244 and JP-A-58-10
Thiazolylbenzimidazole compounds as shown in No. 5145, isothiazolone compounds as shown in JP-A No. 57-8542, lolophenol compounds typified by trichlorophenol, bromophenol compounds, organic Tin compounds, thiocyanic acid and isothyanic acid compounds, acid amide compounds, diazine and triazine compounds, thiourea compounds, alkylguanidine compounds, quaternary ammonium salts such as benzalkonium chloride, and penicillin. antibiotics, active halogen compounds such as sodium hypochlorite and chlorinated sodium isocyanurate, general-purpose disinfectants, anti-inflammatory agents, and "Chemistry of antibacterial and anti-mold" by Hiroshi Horiguchi.
One or more compounds described in Sankyo Publishing (1982) may be used in combination. In particular, combination use with active halogen compounds, thiazolylbenzimidazole compounds, and isothiazolone compounds is preferred.

In addition, various compounds may be added to the washing or stabilizing liquid of the present invention. For example, hardening agents such as magnesium salts and aluminum salts, surfactants to prevent drying load and unevenness, fluorescent whitening agents to improve whiteness, sulfites as preservatives, etc. It is. Orri, E, Wes) (West), 'Water Quality C
r1teria) ``Photographic Science and Engineering (Photo, sci, an
dEng, ), Volume 9, I', 6 (1965), etc. may be added.

In particular, in order to further improve the stability of the washing water, it is preferable to use it in combination with a surfactant. Examples of the surfactant include anionic, cationic, nonionic, and amphoteric surfactants, and particularly preferred are anionic surfactants, especially those having a sulfonic acid group.

In the present invention, the stabilizing liquid is a liquid that has an image stabilizing function that cannot be obtained by washing with water, and for this purpose, a component that stabilizes the image is added in addition to the components added to the washing water. It is something.

Examples of these components include formalin, bismuth salt, aqueous ammonia, and a solution containing ammonium 1.

The pI (pI) of the washing water or stabilizing liquid in the present invention is usually around 7, but it may become pH 3 to 9 due to the water brought in from the previous bath.
0°C, preferably 10°C to 35°C. If necessary, a heater, temperature controller, circulation pump, filter, floating pig, squeegee, etc. may be provided in the washing tank or stabilization tank.

The processing method of the present invention can be applied to any of general silver halide color light-sensitive materials such as color negative film, color paper, color positive film, and color reversal film, but color paper and color negative film are particularly preferred.

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

A6 Color development - Bleach fixing - Washing - Drying - B8 Color development - Bleach fixing - Washing - Stabilizing - Drying E9 color development - Bleach constant fixing - Water washing - Drying F1 color development - Water washing - Bleach constant fixing - Water washing - Drying Drying ■ 0 Color development - Bleach - Bleach fixing Constant fixing - Washing - Stabilizing - Drying J0 Color development - Bleach - Bleach fixing Constant fixing ~ Washing - Drying In the above steps, if the step before the stabilization step is the washing step , the water washing step can be eliminated and the stabilization step performed directly.

The color developing solution used in the present invention contains a color developing agent. Preferred examples are p-phenylenediamine derivatives, and representative examples are shown below, but the invention is not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-6N-ethyl-N-(β-methanesulfonamidoethyl )-3-Methyl-4-aminoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl- N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-ethoxyethylaniline D-1) 4-amino-3-methyl-N-ethyl-N-β
The p-phenylenediamine derivatives of -butoxyethyl esters, collec et al. may be salts such as sulfate, hydrochloride, sulfite, p-)luenesulfonate, and the like. The above compound is described in U.S. Pat.
No. 3,015, No. 2,552,241, No. 2,566
．． No. 271, No. 2,592,364, No. 3.656,
No. 950, No. 3,698,525, etc. The amount of the aromatic-grade amine developing agent to be used is as follows: 1)
About 0.1g to about 20g, more preferably about 0.5g
~10g concentration.

The color developing solution used in the present invention may contain well-known hydroxylamines.

Although hydroxylamines can be used in the free amine form in color developers, it is more common to use them in the form of water-soluble acid salts. Common examples of such salts are sulfates, oxalates, chlorides,
These include phosphates, carbonates, acetates, and others. The hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of the hydroxylamines may be substituted with an alkyl group.

The color developing solution used in the present invention preferably has a pH of 9 to
12, more preferably 9-1). 0, and the color developer may contain other known developer component compounds.

For example, alkaline agents, p■ mild buffer colors, such as caustic soda, caustic potash, soda carbonate, potassium carbonate, tertiary sodium phosphate, tertiary potassium phosphate, potassium metaborate, borax, etc., are used alone or in combination. In addition, disodium hydrogen phosphate or potassium may be added for the purpose of providing buffering capacity, for formulation convenience, or to increase ionic strength.
Various salts are used, such as potassium or sodium dihydrogen phosphate, sodium bicarbonate or potassium boric acid, alkali nitrates, alkali sulfates, and the like.

In addition, various chelating agents can be used in the color developing solution to prevent precipitation of calcium and magnesium. For example, polyphosphates, aminopolycarboxylic acids, phosphonocarboxylic acids, aminopolysulfonic acids, 1-hydroxyalkylidene=1. ■-Diphosphonic acid frequently occurs.

Any development accelerator can be added to the color developing solution if necessary. For example, U.S. Patent No. 2,648,604,
4-9503, various birimidium compounds represented by U.S. Patent No. 3,171,247, other cationic compounds, cationic dyes such as phenosafranin,
Neutral salts such as thallium nitrate and potassium nitrate,
-9304, U.S. Patent No. 2,533,990, U.S. Patent No. 2,
No. 531,832, No. 2.950,970, No. 2.5
Nonionic compounds such as polyethylene glycol and its derivatives described in No. 77.127, polythiol ethers, and thioether compounds described in U.S. Pat. No. 3,201,242 may be used.

Additionally, sodium sulfite, potassium sulfite, potassium bisulfite, or sodium bisulfite, which are commonly used as preservatives, can be added.

In the present invention, any antifoggant can be added to the color developing solution if necessary. As antifoggants, alkali metal halides such as potassium bromide, sodium bromide, potassium bromide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole,
6-nitroindazole, 5-nitroindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2
-Nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and 1-phenyl-5-
Mercapto-substituted heterocyclic compounds such as mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, as well as mercapto-substituted aromatic compounds such as thiosalicylic acid can be used.

Particularly preferred are nitrogen-containing heterocyclic compounds.

These antifoggants may be eluted from the color photosensitive material during processing and may accumulate in the color developer.

The bleaching solution or bleach-fixing solution used in the present invention contains an iron complex as a bleaching solution. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01
~1.0 request o 7! /12 preferably 0.05-0.
It is 50moJ/1. Further, thiosulfate is included as a fixing agent in the fixing solution or bleach-fixing solution. Particularly preferred is ammonium thiosulfate, and the amount added is 0.
．． 1~5.0LIio7! /7! , preferably 0.5~
2.0moj! /J. As a preservative, sulfites are commonly added, but other preservatives include ascorbic acid,
A carbonyl bisulfite adduct or a carbonyl compound may be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, U.S. Pat.
Publication No. 630, Research Disclosure No. 1712
Compounds having a mercapto group or disulfide group described in No. 9 (July 1978 issue), JP-A-5O-44OT
Thiazolidine derivatives described in Publication Z9, U.S. Patent No. 3
, 706.561, iodides as described in JP-A-58-16235, polyethylene oxides as described in German Patent No. 2.748.430, JP-B-Sho. 45- Polyamine compounds described in Japanese Patent No. 8836 can be used.

Furthermore, benzyl alcohol may be used in the color developing solution. Although the present invention is sufficiently effective even in the presence of benzyl alcohol, the water saving effect can be more effectively achieved in the absence of benzyl alcohol.

The present invention will be specifically explained below using Examples.

Example 1 On a subbed cellulose triacetate film support,
A color negative film consisting of each layer having the composition shown below was prepared.

(Composition of photosensitive layer) Coating amounts are expressed in g/l of silver for silver halide and colloidal silver, and g/m'' for couplers, additives and gelatin. , and for sensitizing dyes, silver halide 1 in the same layer
Expressed in moles per mole.

1st layer (antihalation layer) Black colloidal silver...0.4 Gelatin...1.3 Colored coupler〇-1...0.06 Ultraviolet absorber UV-1...0
．． 1 Same as above UV-2-...0.2 Dispersion oil Oi l-1...0. O1 same as above 0i
1-2...0.01 Second layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ)...0.15 Gelatin...1.0 Colored coupler〇-2...0 .02 Dispersion oil Oi I-1...
・0.1 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, diameter/thickness ratio 2.5
Average particle size 0.3μ) ... Silver 1.5 Gelatin ... 0.6 Sensitizing dye I ... 1.0X10-' Sensitizing dye ■
...3.0X10-'sensitizing dye■
・・・lXl0-5゛Coupler C-3・・
・0.06 Coupler C-4...0.06 Coupler C-8...0.04 Coupler C-2...0.03 Dispersion oil 0i1-1...0.03 Same as above O
i 1-3...-0,012 Fourth layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, diameter/thickness ratio 3.5
Average particle size 0.5μ) ...1.5 Sensitizing dye l ...lXl0-' Sensitizing dye ■ ...3 X 10-' Sensitizing dye ■ ...lXl0-5 Coupler C-
3...0.24 Coupler C-4...0.24 Coupler C-8...0.04 Coupler C,-2...0.04 Dispersion oil 01l-1...0.15 Same as above 0il-3...0.02 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 mol%, diameter/thickness ratio 1.
5 average particle size 0.7 μ) ... Silver 2.0 Gelatin ... 1.0 Sensitizing dye■
...lXl0-'sensitizing dye■
...3X10-'sensitizing dye■
...lXl0-'Coupler C-6...0.05 Coupler (, -7...0.1 Dispersion oil 0il-1...0.01 Same as above 0i1-2...0.05 6th Layer (middle layer) Gelatin...1.0 Compound Cp
c5A...0.03 dispersion oil 041
-1...0.05 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, diameter/thickness ratio 2.5
Average particle size 0.3μ) ...0.7 Sensitizing dye ■ ...5X10-' Sensitizing dye V ...0.3X10-' Sensitizing dye ■
...2X10-'gelatin
...1.0 Coupler C-9...0.2 Coupler C-5...0.03 Coupler C-1...0.03 Dispersion oil 0il-1...0.5 8th layer (Second green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 5 mol%, diameter/thickness ratio 3.5
Average particle size 0.5μ)...1.4 Sensitizing dye ■...5X10-' Sensitizing dye V...2X10-' Sensitizing dye ■
...0.3X10-4 coupler C-9.
...0.25 Coupler C-1...-0,03 Coupler C-10...0.015 Coupler C-5...0.01 Dispersion oil 0il-1...0.2 9th layer ( Third green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 mol%, diameter/thickness ratio 1.
5 Average particle size 0.7 μ) ... Silver 1.9 Gelatin ... 1.0 Sensitizing dye■
...3.5X10-'sensitizing dye■
...1.4XlO-' coupler C-1)
...0.01 Coupler C-12...0.03 Coupler C-13...0.20 Coupler C-1...0.02 Coupler C-15...0.02 Dispersion oil 0il-1 ...0.20 Same as above Qil-2...0.05 10th layer (yellow filter single layer) Gelatin ...1.2 Yellow colloidal silver ...0.16 Compound cp d-
B...0.1 dispersion oil 0il-1.
...0.3 1st) layer (first blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, diameter/thickness ratio 1.5, average grain size 0.3 μ) ... Silver 1.0 Gelatin...1.0 Sensitizing dye■
...2X10-' coupler C-14
...0.9 Coupler C-5...0.07 Dispersion oil 0il-1...0.2 12th layer (second blue-sensitive emulsion layer) Silver iodobromide (silver iodide 10 mol%, Diameter/thickness ratio 1.5 Average particle size 1.5 μ) ... Silver 0.9 Gelatin ... 0.6 Sensitizing dye■
...lXl0-' coupler C-14
...0.25 Dispersion oil 0il-1 ...0.07 13th layer (first protective layer) Gelatin ...0.8 Ultraviolet absorber UV-1 ...0.1 Same as above UV-1. ...0.2 Dispersion oil Of+-1...0.01 Dispersion oil Oil-2...0.01 14th layer (second protective layer) Fine grain silver bromide (average particle size 0.07μ) ...・0.5 Gelatin...0.45 Polymethylmethacrylate particles (diameter 1.5μ)...0.2 Hardener H-1...0.4 Formaldehyde scavenger S-1...・0.5 〃 S-2...0.5 In addition to the above-mentioned components, a surfactant was added as a coating aid to each layer. Sample 10 was prepared as above.
It was set to 1.

Next, the chemical structural formulas or chemical names of the compounds used in this example are shown below: UV-1 UV-2 0it-1 Tricresyl phosphate 0it-2 Dibutyl phthalate 0i1-3 Bis(2-ethylhexyl phthalate) E m5 CH2 C(CH3)3 E C-12 CE Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ (CHz) 2S03+1 Sensitizing dye■ ■ CH,= CH-5o□-CHz-CONH-CHzCI
l□=C■-3o2-C1lz-CONH-CHzυ1
) The color negative film created in this way was
After cutting into 1), a standard subject was photographed outdoors, and processed according to the processing steps listed in Table 1 using an automatic processor.

Table 1 Processing Steps The processing temperatures above bleaching, water, and bleaching are 38°C for color development, bleaching, and bleach-fixing, and 35°C for washing.

In the above treatment, water washing (1), (2), and (2) were performed using a multistage countercurrent method.

Also, the overflow of the bleaching solution was introduced into the bleach-fixing solution.

The composition of the treatment liquid used in this treatment is described below.

(Color developer) Mother solution (g) Replenisher (g) Diethylene 1.0 1.1 Triaminepentaacetic acid 1-hydroxy 2.0 2.2 Ethylidene-1゜1-diphosphonic acid sodium sulfite 4.0 4.4 Carbonic acid Potassium 30.0 32.0 Potassium Bromide
1.4 0.7N Tenka Potassium 1.3
mg-hydroxyamine 2.4 2.64
-(N-Ethyl-N-β-hydroxyethylamino)-2- Add methylaniline sulfate solution 17!1) pH 10,0010,05 (Bleach solution) Common to mother liquor and replenisher solution (g) Ammonium bromide 100 Ethylenediamine 120 Ferric ammonium tetraacetic acid salt Ethylene diamine tetra 10.0 Disodium acetic acid salt Ammonium nitrate 10.0 Bleaching accelerators listed below 2.0 Terminated water
IT, add Qmffi water
1) ρ1)
6.5 (bleach-fix solution) Mother liquor (g) Replenisher (g) Ammonium bromide 50.0 -Ethylenediamine tetra 50. O- Ferric ammonium acetate salt ethylenediamine 4 5.0 1. Og disodium acetate salt Sodium sulfite 12.0 20.0 Ammonium thiosulfate aqueous solution (70%) 240mA 400m7!
Ammonia water 10.0 ml Add water
17! 17! pn
7.3 8.0 (Washing water) Common to mother liquor and replenisher Ethylenediaminetetraacetic acid di-sodium salt 0.35 g Polyoxyethylene-p -0.30 g Monononylphenyl ether (Average degree of polymerization 10) Add water 1 ) The treatments listed in Table 2 were performed using the above treatment steps and treatment agents.

All treatments were started from fresh solutions.

The processing speed was 50 m/hour in both cases.

Table 2 (ratio) tank,
The second washing tank and the third washing tank form a three-stage countercurrent washing tank. A is the overflow of the first washing tank, B is the storage tank, F
is a reverse osmosis treatment device, C is permeated water, D is concentrated water, G is supplementary washing water, S8 and S2 are float switches that start and stop the liquid pump P, and P starts with Sl and stops with S2. .

The diagonal pipe connecting T, and T2, and T2 and T3 is from T3 to Tz
, Tw is a conduit through which liquid flows from T. The reverse osmosis treatment equipment was equipped with a tubular type cellulose acetate reverse osmosis membrane with a membrane area of 0.86 m'', and was operated at a pressure of 20 kg/-.

This reverse osmosis treatment equipment was operated only during treatment.

The amount of permeated water at a pressure of 20 kg/cta gradually decreases as the treatment progresses because the concentration of liquid flowing into the reverse osmosis device increases, and in treated tooth 4, the average on the first day is 100 mn/min and the average on the 14th day is 85mj! /min, the average on the first day for treated tooth 5 is 100m 17 minutes, 14
The daily average is 60ml! It was 7 minutes.

On the other hand, regarding the amount of concentrated liquid discharged on treated tooth 4, the average on the first day was 200 mβ/min, and the average on the 14th day was 220 mj! /min, processing 1) average of 200 mn on the first day at kL5
/min, the 14-day average is 240m7! /minute.

The removal efficiency of the reverse osmosis treatment equipment remained above 99% for iron, silver, and thiosulfate during the entire period.

After each process, the color negative film has a color fade of 480 degrees.
0 was treated with wedge exposure at an exposure dose of 20 CMS, and the fading of the cyan dye at an initial density of 1.5 during storage at 80° C. for 3 hours was investigated, and the results are listed in Table 3.

Table-3 As shown in Table-3, according to the three-stage countercurrent water washing system,
At 35m/m, water can be saved up to 30ml per 1m of film without any problem, but 6m! ! Doing so will increase fading and make it impossible to save water. The processing tooth 4 is a method in which the overflow of washing water is directly reverse osmosis treated without providing a storage tank in the conventional method. The amount of water discharged as concentrated liquid increases, and the amount of permeated water supplied decreases.
The inside of the washing tank cannot be purified and water cannot be saved. In contrast, according to the method of the present invention, the concentrated liquid is circulated between the storage tank and subjected to reverse osmosis treatment repeatedly, making it possible to sufficiently increase the degree of concentration even in a small device like the one in this embodiment. , water loss is extremely low and water can be saved.

Example 2 In Example 1, the composition of the washing water was changed as shown in Table 4, and sodium hydroxide was added to pn7. o, and then reverse osmosis treatment was performed using the method of Example 1 treatment Na5 to examine changes in the amount of permeated water.

The composition of the supplementary washing water was also as described in the column of washing water composition in Table 4.

Except for the above, the treatment was carried out in the same manner as in Example-1.

After 14 days, the amount of permeated water from the reverse osmosis treatment equipment was measured using the reverse osmosis membrane that had been used for treatment and the same unused reverse osmosis membrane, and the ratio to the amount of permeated water from the unused membrane was measured in Table 4. It was shown to.

Table 4 As shown in Table 4, it can be seen that in the present invention, when the compounds described in 1lk4 to Na6 are added to the washing water, the decrease in the amount of permeated water is extremely reduced.

Example 3 The reverse osmosis treatment equipment was installed as shown in Figure 3, a stabilizing bath was provided in the final step, the treatment process was as shown in Table 5, and the composition of the washing water was as shown below. Example-1, Processing The same processing as NFL5 was performed.

<Washing water composition> Ethylenediamine tetra 0.3g per washing water 1) Acetic acid di-sodium salt <Stabilizing liquid composition> Mother liquor (g) Replenishment solution (g) Formalin (37% w/v) 2.0 m 7!3 .0
ml polyoxyethylene 0.3 0.4
5-p-monononylphenyl ether (average degree of polymerization 10) Add water 17! The stabilizing liquid composition is 20 m/m of film with a width of 35 m/m.
j! And so.

The meanings of the symbols in FIG. 3 are the same as in FIG. 2.

Table 5 After 14 days of treatment, the same fading test as in Example 1 was conducted, and the same results as in Example 1 and Treatment No. 5 were obtained.

Example-4 Table A was placed on a paper support laminated on both sides with Boeethylene.
A multilayer color photographic paper with the layer structure shown below was prepared. The coating solution was prepared as follows.

Preparation of first layer coating solution To 9.1 g of yellow coupler + al l and 4.4 g of color image stabilizer (b), 21.2 m (l) of ethyl acetate and 9 ml of solvent (C17, 1 l) were added and dissolved.
The mixture was emulsified and dispersed in 185 m# of a 10% gelatin aqueous solution containing 8 mA of sodium dodecylbenzenesulfonate. On the other hand, silver chlorobromide emulsion (silver bromide 4IIlo1%, 70g/
kg) and the blue-sensitive sensitizing dye shown below was added to silver chlorobromide.
5. per lol. 90g of a blue-sensitive emulsion was prepared by adding OXlO-'mail. The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table 1 to prepare a first layer coating solution. The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. ■-Oxy-3,5-dichloro-5-1-riazine sodium salt was used as the gelatin hardening agent for each layer.

The following spectral sensitizers were used in each emulsion.

Blue-sensitive emulsion layer Green-sensitive emulsion layer (7. OX 10-5 mo per 1 mo β of silver halide
/ Addition) Red-sensitive emulsion layer (1. OX 10-' per 1fflor of silver halide)
moA' Addition) The following dyes were used as irradiation-preventing dyes in each emulsion layer.

Green-sensitive emulsion layer: Red-sensitive emulsion layer: The structural formulas of the compounds used in this example, such as couplers, are as follows.

(al yellow coupler 6.7! (b1 color image stabilizer (C) solvent tel magenta coupler (M53) tf1 color image stabilizer 2:1 mixture (weight ratio) (hl 1:5:3 mixture of ultraviolet absorber ( Molar ratio) (1) Color mixing prevention agent 1'1ll OI amount + 31 solvent (iso Cgll 1sOhP = 0 Hitoshi Gogo) Color photographic paper made as above is 82.5n+/n
+1), exposed to light using an automatic printer, and processed according to the processing steps listed in Table 6 using an automatic processor.

Table-6 Treatment process The formulations of each treatment liquid used are as follows.

Color developer mother solution replenisher water
800m/ 800mA Lithium chloride 1.0 g 1.0 g Diethylene] Liamine Ig Ig Pentaacetic acid, 5-dihydroxy 1.0 g 1.5 g-
Sodium sulfite m-benzenedisulfonate 0.5 g 1.0
g Potassium bromide 0.1g - Sodium chloride 1.5g - Adenine
30mg 60B potassium carbonate
40g 40gN-x Chill-N-4,
5g l 1. Og (β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate hydroxylamine 3.0 g 4.0
g Sulfate fluorescent whitening agent (Jumin Chemical 1.0g 2.0gG
IWhitex 4) Poly (ethyleneimine) 3.0g 3.
0g (50% aqueous solution) Add water to 1000m7! 100100O
In OH pHI O, 25p) II O, 8
0 Bleach-fix solution Mother solution Replenisher water
700mn 700 ammonium thiosulfate 150mff 200mff (70
%) Sodium sulfite 18g 25g Ethylenediamine tetra 55g 65g Iron acetate (II
I) Ammonium ethylenediamine 4 5g 10g Acetate pH 6,756,50 with aqueous ammonia or acetic acid Add water to 10100O! 1000m#
Stabilizing solution (common to mother solution and replenisher) ■-Hydroxyethylidene-1.1 1.5m7! −
Diphosphonic acid (60%) Nitrilotriacetic acid 1.0g Ethylenediaminetetraacetic acid 0.5g N, N, N'
, N'-tetramethy 1.0g Renphosphonic acid B1Cl1z (40% aqueous solution) 0.5
0 gMgSO4・7HzOO, 20g ZnSO40, 3g Ammonium Alum 0.5g 5-Chloro-2-methyl-4-iso 30mg Thiazoline 3
-one 2-methyl-4-isothiazoline-10mg3-one 2-octyl-4-isothiazoline 10mg-3-
Ethylene glycol 1.5g Sulfanilamide 0.1g 1.2.3-
Benzotriazole 1.0g Ammonium sulfite (40% aqueous solution) 1.0g Aqueous ammonia (26%
) 2.6 m 7! Polyvinylpyrrolidone 1.0g Fluorescent brightener (4,4'
-Diamino 1.0g stilbene type) Add water 100100OOH
At r+I+7.0 or higher, the treatments listed in Table 7 were carried out using the second treatment step and treatment solution. All treatments in Table 7 were started from fresh solutions.

Further, the processing speed was 120 m/hour.

Table 7 The reverse osmosis treatment used was the same as that described in Example-1.

The treated paper at the end of each treatment was stored at 60°C at 70% for 4 weeks, and the increase in yellow stain during this period was examined, and the results are listed in Table 8.

The meanings of the symbols in FIGS. 4 and 5 are the same as in FIG. 2.

Table 8 As described above, it can be seen that according to the present invention, yellow stain does not increase even if the amount of stabilizing liquid water is greatly reduced.

Example 5 Using the multilayer color photographic paper described in Example 4, the treatments described in Table 9 were carried out.

Table-9 Treatment process The composition of the treatment liquid used in the above treatment is as follows.

+1) Color developer Same as Example 4 (2) Bleach-fix solution Mother solution Replenisher water
700m7! 500m
nAmmonium thiosulfate 150mA 300mn (
70%) Sodium sulfite 18g 36g Ethylenediaminetetraacetic acid 55g 1) 0g Iron(II+)
Ammonium ethylenediaminetetraacetic acid 5g 10g with ammonia water or acetic acid pl+ 6.75 6.50 Add water 10100O! 10100O! (
3) Washing water Tap water is softened using a strong acid cation exchange resin (Na type) Diaion 5K-IB (manufactured by Mitsubishi Kasei).

The treatments listed in Table 10 were performed using the above treatment steps and treatment solutions.

Table 10 The reverse osmosis treatment equipment used was equipped with a spiral type cellulose acetate reverse osmosis membrane with a membrane area of 1.2 m, and an initial permeate flow rate of 350 ml/min was obtained at a pressure of 14 kg/cJ. At this time, the concentrated discharge amount was 400 m 17 minutes.

In Figure 5-A and B, Ll is a color developer tank, B2
Bleach-fix solution tanks TI, T2, and T3 indicate first, second, and third washing tanks, respectively.

A is the overflow liquid from the second washing tank, B1) B2 is the storage tank, C is the permeated liquid, D is the concentrated liquid, F is the reverse osmosis treatment device, P, , P is the liquid sending pump, and H is T.

The liquid in B2 is introduced into , G is newly supplied washing replenishment water, Sl, B2, B3, B4 are P, , P.

This is a float switch that starts and stops the

PI, P, S+, Ss "i1' start, B2, B
Stop at 4.

The diagonal pipe connecting B2 and T, T2 and T3 is T.

This is a conduit for flowing liquid from T z to B2 and from T + to B2.

Incidentally, in Th4.1) h5, the overflow liquid from the storage tank was introduced into the first washing tank, and the overflow liquid from the first washing tank was further introduced into the bleach-fixing bath. For each treatment, the state of the yellow stain immediately after the treatment on the 14th day was shown as the difference from the yellow stain immediately after the treatment at the start of each day, and is listed in Table 1).

Table 1) As shown in Table 1), according to the present invention, it is possible to perform treatment without increasing yellow stain even when water is saved.

[Brief explanation of drawings]

Figure 1, Figure 2-B, Figure 3, Figure 4-B and Figure 5-
B is a diagram showing the processing method of the silver halide color photographic light-sensitive material of the present invention, and FIG. 2-A, FIG. 4-A, and FIG. It is a figure showing the processing method of materials. A... Overflow liquid B... Storage tank C... Permeated liquid D... Concentrated liquid E... Reverse osmosis treatment device F... Reverse osmosis membrane T... Washing tank Figure 5-A

Claims (3)

[Claims] (1) In a method in which a silver halide color photographic light-sensitive material is processed in a bath having fixing ability and then washed and/or stabilized in a multi-stage countercurrent method, the overflow liquid from the washing tank and/or stabilization tank is stored. A halogenation method characterized by introducing the liquid into a tank, subjecting the liquid in the storage tank to reverse osmosis treatment, returning the permeated liquid in the reverse osmosis treatment to the washing tank and/or stabilization tank, and returning the concentrated liquid to the storage tank. Processing method for silver color photographic materials. (2) In the water washing and/or stabilization tank, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, 1,3-diaminopropanetetraacetic acid, and salts thereof, and the following general formulas (I) and (II) The method for processing a silver halide color photographic light-sensitive material according to claim (1), characterized in that it contains at least one compound selected from the compounds represented by the following. General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3, R_4 and R_5 are hydrogen atoms, halogen atoms, alkyl groups, substituted alkyl groups, hydroxyl groups, amino groups, nitro (In the formula, R_6 and R_7 are hydrogen atoms, alkyl group, substituted alkyl group, aryl group, substituted aryl group, or nitrogen-containing heterocyclic group) (3) Claims (1) or (2) characterized in that the liquid in the storage tank is introduced into a bath having fixing ability.
) A method for processing a silver halide color photographic light-sensitive material.