JPH0436376B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a method for processing a silver halide color photographic light-sensitive material (hereinafter abbreviated as light-sensitive material), and particularly to a stabilization processing method that does not involve a water washing step following a desilvering step. [Prior Art] In recent years, environmental conservation and water resource issues have become important in photofinishers that automatically and continuously develop photosensitive materials. It is desired to reduce or eliminate the large amount of washing water used in the process. For this reason, a technique has been proposed in which a stabilization treatment is performed directly after fixing or bleach-fixing without washing with water. For example, JP-A-57-8542, JP-A No. 57-8542;
-132146, No. 57-14834, and No. 58-18631 each describe a technique of processing with a stabilizing solution containing an isothiazoline derivative, a benzisothiazoline derivative, a soluble iron complex salt, a polycarboxylic acid, and an organic phosphonic acid. There is. These techniques relate to methods for suppressing or preventing problems caused by fixing and bleach-fixing components introduced by photosensitive materials into the stabilizing solution; If the concentration exceeds a certain level, it cannot be put to practical use, and a certain amount of stabilizing solution must be replenished. In particular, when the concentration of the fixing and bleach-fixing components in the final stabilizer bath increases, yellow stains in unexposed areas of the photosensitive material due to long-term storage increase. Another problem is that if the waterless washing stabilization treatment is carried out continuously for a long period of time, the amount of staining in the unexposed areas immediately after the treatment increases, regardless of the amount of fixing and bleach-fixing components mixed in. I understand. OBJECTS OF THE INVENTION Accordingly, a first object of the present invention is to provide a problem-free color stabilization process by reducing the concentration of fixing and bleach-fixing components in the stabilizing solution. A second object of the present invention is to provide a color stabilization processing method that does not increase staining in unexposed areas immediately after processing even if continuous processing is performed for a long period of time. A third object of the present invention is to reduce the amount of replenishment of the stabilizing solution by removing harmful components in the stabilizing solution;
Another objective is to provide a reusable method. [Summary of the Invention] A method for processing a photosensitive material according to the present invention to achieve the above object is to process a photosensitive material with a processing liquid having a fixing ability and then stabilize it with a stabilizing liquid without substantially washing with water. In the method of processing photosensitive materials,
The stabilizing solution is characterized in that it contains a chelating agent having a chelate stability constant of 6 or more with ferric ions, and that the stabilizing solution is subjected to reverse osmosis treatment. [Structure of the Invention] The present invention will be explained in more detail below. In a process that involves a normal water washing process, fixing, bleaching and fixing components, eluates from photosensitive materials, fatigue components, etc. are all washed away in the water washing process, but when directly stabilized without going through the water washing process, , all accumulate in the stabilizing solution, resulting in yellow stains during long-term storage and stains immediately after processing. As a result of extensive research, the inventors of the present invention have discovered that this can be prevented by subjecting the stabilizer to reverse osmosis treatment. In the reverse osmosis treatment used in the present invention, conventionally known reverse osmosis membranes, desalination/concentration methods and devices using reverse osmosis membranes can be used without restriction. As the reverse osmosis membrane, cellulose acetate, aromatic polyamide, polyvinyl alcohol, and polysulfone are preferable, and cellulose acetate is particularly preferably used. Modules using these reverse osmosis membranes include Toyobo Co., Ltd., Toray Industries, Inc., Du Pont, and
There are products made by Paterson Oandy International, etc.
Furthermore, devices used for reverse osmosis treatment (hereinafter abbreviated as reverse osmosis devices) are manufactured and sold by Sasakura Kikai Co., Ltd., Kurita Industries Co., Ltd., Eberrein Filco Co., Ltd., and others. The reverse osmosis device is preferably operated at a pressure of 40 Kg/cm ² to 55 Kg/cm ² from the viewpoint of separation performance and processing capacity. In the present invention, reverse osmosis treatment has made it possible to prevent staining, which is the main purpose of the present invention.
A chelating agent is contained in the stabilizing liquid to further ensure this stain prevention effect. The type of chelating agent and the stain prevention effect are related to the chelate stability constant of the chelating agent with iron ions, and in particular, it is recommended to use a stabilizing solution containing a chelating agent with a chelate stability constant of 6 or more with iron ions. A remarkable stain prevention effect can be obtained by reverse osmosis treatment. The term "chelate stability constant" here indicates the stability of a complex formed by a metal ion and a chelate in a solution, and means a constant defined as the reciprocal of the dissociation constant of the complex, LGSille' n AE Martell, “Stability
Constants of Metal−ion Complexes”，The
Chemical Society, London (1964), S. Chaberek AE Martell, “Orgnic
Chelating agents having a chelate stability constant of 6 or more with iron ions that are preferably used in the present invention include organic carboxylic acid chelating agents and organic phosphoric acid chelating agents. Among them, preferred chelating agents include ethylenediamine diorthohydroxyphenylacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, trans Cyclohexanediaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, 1,1'-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-
1,2,4-tricarboxylic acid, 1-hydroxy-
Examples include 1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate, and particularly preferred are diethylenetriaminepentaacetic acid and 1-hydroxyethylidene. -1,1'-diphosphonic acid or a salt thereof. The amount of the above chelating agent added is 0.01 per stabilizer.
g to 100 g, particularly preferably 0.1 g to 20 g.
Furthermore, the timing and method of addition are not particularly limited. Further, desirable compounds to be added to the stabilizer of the present invention include PH adjusters such as acetic acid, sulfuric acid, hydrochloric acid, nitric acid, sulfanilic acid, potassium hydroxide, sodium hydroxide, ammonium hydroxide, sodium benzoate, hydroxyl, etc. butyl benzoate, antibiotics,
Anti-bacterial agents such as dehydroacetic acid, potassium sorbate, thiabendazole, ortho-phenylphenol, 5-chloro-2-methyl-4-thiazolin-3-one, 2-octyl-4-isothiazolin-3-one , 1,2-benzisothiazolin-3-one, preservatives such as aqueous metal salts, dispersants such as ethylene glycol, polyethylene glycol, polyvinylpyrrolidone, hardeners such as formalin, fluorescent brighteners, etc. . The most effective of these compounds is
It is an ammonia compound described in the specification of No. 58-58693 (see JP-A-59-184345). In the treatment method of the present invention, the pH value of the stabilizing solution is PH
It is best to adjust the pH to 0.1-10, preferably PH2-10.
9, more preferably PH6 to 8.5. The processing temperature during stabilization treatment is 15°C to 60°C.
℃, preferably in the range of 20℃ to 45℃. In addition, from the viewpoint of rapid processing, it is preferable that the processing time be as short as possible, but it is usually 20 seconds to 10 minutes, most preferably 1 minute.
minutes to 5 minutes, and in the case of multiple tank stabilization treatment, it is preferable that the earlier stage tanks be treated for a shorter time and the later stage tanks be treated for a longer time. In particular, it is desirable to process sequentially with a processing time 20% to 50% longer than in the previous tank. Further, it is preferable that the stabilization treatment process be carried out in a multi-stage tank, and the replenisher is replenished from the last stage tank, and a backflow method is used in which it sequentially overflows into the previous stage tank. After the stabilization treatment according to the present invention, there is no need for any water rinsing treatment, but rinsing by rinsing with a small amount of water within an extremely short period of time, surface cleaning, etc. can be optionally performed as necessary. The treatment step having a fixing ability in the present invention is aimed at desilvering, and specifically involves treatment in a bleach-fixing bath, a fixing bath, or the like. The bleaching agent used in the present invention is not particularly limited, but is particularly effective when using an organic acid ferric complex salt, and the fixing agent is also not limited, but it is particularly effective when using a thiosulfate. It is particularly effective when using a fixing bath or a bleach-fixing bath containing an organic acid ferric complex salt and a thiosulfate. In the present invention, performing the stabilization treatment without substantially washing with water following the fixing treatment step means a short-time silver recovery bath for recovering silver between the fixing bath or bleach-fixing bath and the stabilization treatment. This means that rinsing etc. may be provided. It also means that after the stabilization treatment, a draining bath containing a surfactant or the like may be provided, but preferably,
In order to speed up and simplify the process, it is preferable not to provide a silver recovery bath, rinsing bath, draining bath, etc. The method of bringing the stabilizing solution of the present invention into contact with the photosensitive material is to immerse the photosensitive material in the solution in the same way as a general processing solution. It may be applied to both sides and the conveyor belt, or it may be sprayed onto the conveyor belt. In the present invention, the stabilizing liquid is subjected to reverse osmosis treatment.
Treatment methods include a method in which the stabilizing solution in the stabilizing bath is continuously treated and a method in which the overflow is treated and the diluted solution is returned to the stabilizing bath, but the latter method is more preferable. Note that as a pretreatment for the reverse osmosis treatment, a treatment means such as a sand filter or a precoat filter may be provided. This is to prevent a decrease in capacity due to clogging of the reverse osmosis membrane. If microorganisms or the like adhere to the reverse osmosis membrane and cause clogging, measures such as sterilization treatment may be added as necessary. Methods for returning the diluted liquid discharged from the reverse osmosis device to the stabilizing bath include a method in which it is once stored in a storage tank and then returned, and a method in which it is returned directly, but direct return is preferable. When returning the solution after it has been stored in a storage tank, it is preferable to supplement the missing components and return it to the stabilizing bath as a replenisher. The stabilization treatment used in the present invention is carried out in one or more treatment tanks, but
In the case of two or more tanks, the liquid intake and diluted liquid outlet of the reverse osmosis device may be connected to the same stabilizing tank or different stabilizing tanks, but if they are connected to the same stabilizing tank. It is preferable for the tank to be close to the processing tank that has fixing ability, and if it is connected to a different stabilizing tank, the tank that is close to the processing tank that has fixing ability should be connected to the inlet.
It is preferable to connect a remote tank to the diluent outlet. It is preferable that silver is recovered from the concentrate obtained by reverse osmosis, and the silver recovery is preferably carried out by mixing it with a processing liquid having fixing ability. Preferably, the concentrate is also returned to a processing tank having fixing capacity. The diluted liquid is preferably treated with activated carbon by a powder mixture, a fluidized bed or fixed bed type adsorption tower treatment using granular activated carbon, or other known methods. Note that treatment means such as coagulation sedimentation or sand filtering may be added as a pretreatment to the activated carbon treatment. [Examples] Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 An experiment was conducted using Sakura Color Paper (manufactured by Konishiroku Photo Industry Co., Ltd.) as a photosensitive material and using the processing solution and processing steps as described below. Standard processing steps [1] Color development 38℃ 3 minutes 30 seconds [2] Bleach-fixing 33℃ 1 minute 30 seconds [3] Stabilization 25℃~30℃ 3 minutes [4] Drying 75℃~80℃ approx. 2 Separation solution composition <color development tank liquid> Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 1.3g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-Methyl- 4-amino-N-ethyl-N-
(β-Methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4-diaminostilbenzsulfonic acid derivative) 1.0g Catechol-3,5-disulfonic acid 0.3g Add water to bring the total amount to 1 and adjust the pH to 10.00 with KOH. <Color developer replenisher> Benzyl alcohol 22ml Ethylene glycol 2.0ml Potassium sulfite 3.0g Potassium carbonate 30.0g Hydroxylamine sulfate 4.0g Polyphosphoric acid (TPPS) 3.0g 3-Methyl-4-amino-N-ethyl-N-
(β-Methanesulfonamidoethyl)-aniline sulfate 7.5g Fluorescent brightener (4,4-diaminostilbenzsulfonic acid derivative) 1.5g Catechol-3,5-disulfonic acid 0.3g Add water to bring the total amount to 1 and adjust the pH to 10.50 with KOH. <Bleach-fix tank solution> Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to PH7.1 with potassium carbonate or glacial acetic acid Add water to bring the total volume to 1. <Bleach-fixing replenisher A> Ethylenediaminetetraacetic acid ferric ammonium dihydrate 260g Potassium carbonate 42g Add water to bring the total amount to 1. The pH of this solution is 6.7±0.1. <Bleach-fix replenisher B> Ammonium thiosulfate (70% solution) 500ml Ammonium sulfite (40% solution) 150ml Ethylenediaminetetraacetic acid 17g Glacial acetic acid 85ml Add water to bring the total volume to 1. The pH of this solution is 4.6±0.1. <Stable tank fluid and replenisher fluid> Diethylenetriaminepentaacetic acid 2.0g 5-chloro-2-methyl-4-isothiazolin-3-one 0.03g 2-methyl-4-isothiazolin-3-one
Make 1 with 0.03g water. The pH of this solution is 4.0. Experiment 1 In the automatic processor for color paper shown in Fig. 4, color developing tank liquid is placed in color developing tank 1, bleach fixing tank liquid is placed in bleach fixing tank 2, and stabilizing tanks 3A, 3B, and 3C.
Fill the tank with stable tank liquid, and while processing the photoprint-exposed color paper, fill the color developer replenisher tank 1R and bleach-fixer replenisher tank 2 every 3 minutes.
Continuous processing was carried out while replenishing the color developing replenisher, bleach-fixing replenisher A, B, and stable replenisher stored in the RA, 2RB, and stable replenisher tanks 3R through quantitative cups, respectively. The replenishment amounts of color developing replenisher, bleach-fixing replenisher A, and B are 170 ml, 25 ml, and 25 ml, respectively, per 1 m ³ of color paper.
For stable replenisher, per ^1m3 of color paper.
Three points were tested: 100ml, 300ml, and 1. The stabilizing tanks 3A, 3B, and 3C of the automatic processor are the first to third stabilizing tanks in the direction of the flow of the photosensitive material, and the final tank 3C is replenished, and the overflow from the final tank 3C is transferred to the previous tank. Let it flow into 3B,
Furthermore, a multi-stage countercurrent system was adopted in which this overflow liquid also flowed into the tank 3A at the previous stage. Continuous processing was carried out until the total replenishment amount of stabilizing solution reached three times the capacity of the stabilizing tank, and unexposed color paper was processed and used as a sample. For comparison, a sample was prepared in which the stabilization treatment was performed in place of washing with running water. Samples for same-day yellow staining
The reflectance was measured at 445nm and shown in Table 1. Furthermore, due to the yellow stain over time, the reflectance was measured at 70℃ and 80%RH.
After storage for a week, yellow stain was measured using an optical densitometer (PDA-65 manufactured by Konishiroku Photo Industry Co., Ltd.) under blue light, and the results are shown in Table 1. Experiment 2 As shown in Figure 1, an experiment similar to Experiment 1 was repeated using an apparatus in which a reverse osmosis device was attached to the automatic processor for color paper used in Experiment 1. Here, the overflow of the stabilizing liquid from the first tank 3A of the stabilizing tank is sent to the reverse osmosis treatment device 4 through the overflow discharge pipe 3L, and the diluted liquid is sent to the second tank 3B of the stabilizing tank through the diluent discharge pipe 4A. will be returned to. On the other hand, the concentrate is sent to the electrolytic silver recovery device through the concentrate discharge pipe 4B, where it is mixed with the overflow of the bleach-fix solution and electrolyzed silver is recovered. Reverse osmosis equipment uses cellulose acetate-based semipermeable membranes.
0.86m ² Incorporated Paterson Oandy International
A tubular type module made by the company was used. Stabilizing liquid overflow is applied to the above semi-permeable membrane at a pressure of 55 kg/
cm ² and a water flow rate of 4/min. At this time, the amount of water permeated through the membrane was adjusted to 3.2/min to give a recovery rate of 80%. The yellow stain results obtained in the above experiment are shown in Table 1 together with the results when water was added instead of the stabilizer of the present invention.

[Table] As is clear from Table 1, when only the conventional stabilizer was used, both the yellow stain on the same day and the yellow stain after storage worsened as the replenishment amount decreased, especially up to 100ml/ ^m2 . Reducing the amount increases staining significantly more than running water rinsing. Furthermore, even if reverse osmosis treatment is performed, if the replenisher is water, the yellow stain will be high both on the same day and after storage. However, in the treatment method of the present invention, even if the amount of replenisher is reduced to 100ml/ ^m2 , the yellow stain on the same day is equivalent to washing with running water, and the yellow stain after storage is better than washing with running water. It can be seen that the amount and emissions can be reduced. The process of the present invention was also carried out when the diluent discharge pipe 4A was connected to the final tank 3C of the stabilization tank and when it was connected to the first tank 3A, and almost the same results were obtained. Example 2 The treatment was carried out using the treatment apparatus shown in FIG. 2 with the same treatment steps as Example 1 except that the treatment time of the stabilization treatment step was changed to 1 minute. here,
There is one stabilizing tank, and the diluted solution subjected to reverse osmosis treatment is returned to the stabilizing tank via a diluted solution discharge pipe 4A, while the concentrated solution is returned to the bleach-fix tank via a concentrated solution discharge pipe 4B. The processing liquid used was the same as in Example-1 except for the stable tank liquid and stable replenisher liquid. For stable tank fluids and stable replenishment fluids, see Table-
Nos. 1 to 7 shown in No. 2 were used. Further, the reverse osmosis device used and the conditions of use were the same as in Example-1. Table 2 shows the yellow stain results obtained by conducting the same experiment as in Example 1. However, the amount of stable replenisher is 100 per ^m2 of color paper.
For comparison, an experiment was conducted without using a reverse osmosis device, and the results are listed as No. 8 in Table 2.
I wrote it together. Furthermore, Experiment No. 1 of Example-2
(Comparative Example), a chelating agent (glycolic acid, propionic acid) having a stability constant of less than 6 with ferric ion was added, and the other conditions were the same as in Example 2. (Experiment No. 9 and Ten). The results are summarized in Table-2.

[Table] In the table, Experiment Nos. 1 to 8 are Experiment Nos. 1 to 8 of Example-2.
It corresponds to 8. In addition, HEDP is 1-hydroxyethylidene-
1,1-diphosphonic acid, NTPO is nitrilotrimethylenephosphonic acid, HEDTA is hydroxyethylethylenediaminetriacetic acid, GL is glycine,
GA stands for glycolic acid and PA stands for propionic acid. From Table 2 above, it can be seen that the effect of the present invention is remarkable when a stabilizing solution containing a chelating agent having a chelate stability constant of 6 or more with ferric ions is subjected to reverse osmosis treatment. In addition, the diluent discharge pipe 4A has an inner diameter of 200 mmφ and a height of
Column 4 soaked with 500mm coconut shell granular activated carbon
Even better results were obtained when AC was installed. On the other hand, an experiment was also conducted in the case where the concentrate discharge pipe 4B was not connected to the bleach-fixing tank, and results were obtained that were generally the same, although slightly inferior overall. Example 3 The same treatment steps as in Example 1 were carried out using the treatment apparatus shown in FIG. 3, except that the treatment time of the stabilization treatment step was changed to 2 minutes. Here, there are two stabilization tanks, and the diluted solution subjected to reverse osmosis treatment is temporarily stored in the diluted solution storage tank 5 through the diluted solution discharge pipe 4A, and after being adjusted to a stable regenerated replenishment solution, the diluted solution is converted into a stable regenerated replenisher. The stable replenisher tank 3R is sent to the stable replenisher tank 3R via the transfer pipe 5A and is replenished. The processing liquid used was
The same ones as in Example-1 were used except for the stable tank liquid, stable replenisher, and stable regeneration replenisher. For the stable tank liquid, stable replenisher liquid, and stable regenerated replenisher liquid, the formulation No. 7 of Example-2 was used. Further, the reverse osmosis device used and the conditions of use were the same as in Example-1. The experiment was carried out in the same manner as in Example-1, but with regard to replenishment of the stabilizing liquid, 400 ml of stable replenishing liquid was first replenished per 1 ^m2 with the stable replenishing liquid of the fresh, and the amount of stable replenishing liquid was 1 of the tank capacity of the stabilizing tank. /100, add the stored diluent to the stable regeneration replenisher.
A stable regeneration replenisher was made as 75% water and used as the replenisher, and the same operation was then repeated. The amount of replenishment liquid is practically 100ml per ^1m2 ,
The obtained yellow stain results were almost the same as those of Example 2 and were very good.

[Brief explanation of drawings]

1 to 3 are flow sheets showing the processing method of the present invention, and FIG. 4 is a flow sheet showing the processing method using a conventional automatic processor for color paper. In the figure, 1 is a color developer tank, 1L is a color developer overflow discharge pipe, 1R is a color developer replenisher tank, 2 is a bleach-fix tank, 2L is a bleach-fix overflow discharge pipe, 2RA and 2RB are bleach-fix replenisher tanks. , 3, 3A, 3B, 3C are stabilizing tanks, 3L is a stable liquid overflow discharge pipe, 3R is a stable replenishment liquid tank, 4 is a reverse osmosis treatment device, 4A is a diluted liquid discharge pipe, 4B is a concentrated liquid discharge pipe, 5 is a The diluent storage tank and 5A each indicate a regenerated replenisher transfer pipe.

Claims (1)

[Claims] 1. A method for processing a silver halide color photographic material, in which the silver halide color photographic material is processed with a processing liquid having fixing ability and then stabilized with a stabilizing liquid without substantially washing with water. 1. A method for processing a silver halide color photographic light-sensitive material, comprising a chelating agent having a chelate stability constant of 6 or more with diiron ions, and comprising subjecting the stabilizing solution to reverse osmosis treatment.