JPS5860741A - Treatment of developing solution - Google Patents

Abstract

PURPOSE:To maintain bromine ion concn. constant in a developing soln., by mixing a proper amount of developing soln. freed of bromine ions by its separation method with that not freed of the ions, and adding a regenerating agent to obtain a replenishing soln. CONSTITUTION:In the method in which a silver halide color photographic material is developed with a developing soln. contg. 4.6-3.0g/l p-phenylenediamine type color developing agent having at least one water-soluble group, such as formulaIor II or the like in its amino group, 1/10-9/10 part of the total amount of developing soln. flowing out of a developing soln. tank 12 is not freed of bromine ions, and the rest of it is freed of bromine ions by a separation method, such as electrodialysis or ion exchange, then both are mixed, and a regenerating agent is added to obtain a replenishing soln., thus permitting a bromine ion concn. in the tank 12 is held substantially constant to maintain its developing characteristics.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color attenuation development processing method,
More specifically, bromide ions are removed using a separation method,
The present invention relates to an improved color development process that effectively maintains a selected bromide ion concentration constant.

It is generally known that bromide ions are eluted from the light-sensitive material into the developer and accumulated in the developer during the development process of a silver halide photographic light-sensitive material, thereby inhibiting the development reaction.

Therefore, it is necessary to reduce the bromide ion content in the developer and maintain its concentration within a certain range.

In the normal development processing method, as described above, halogen ions are eluted from the silver halide photographic light-sensitive material, and the developing agent, preservative, alkaline agent, etc. are consumed and reduced. Then, in order to keep these concentrations substantially constant and maintain the t# and m characteristics, a replenisher is added to the developer, and the added amount is flowed out of the developer tank system as an over-70 solution.
Bromide ions in the developer are removed from the system. In addition, deficient components such as consumed developing agent are replenished from this replenisher to keep the concentration of the developer constant.

However, in such a method, a large amount of active ingredients such as a developing agent and an alkaline agent are wasted together with the overflow liquid, which is uneconomical and undesirable from the viewpoint of environmental pollution. Therefore, a method was devised in which the bromide ion concentration in the replenisher was reduced or the bromide ion content was not included, and the replenisher was refilled using a small amount of replenisher with a high concentration of replenishment components such as developing agent, thereby reducing the amount of overflow liquid. It was done. Journal of the NIS MBC
of the SMPT11! , Oummins,
Cogan, and Well, 66 (1957 edition) 555) In this method, there is a limit to the solubility of the drug, and if the bromide ion concentration in the replenisher is reduced to zero and the amount of replenisher is reduced, the resulting The bromide ion concentration in the developer increases, and in order to maintain the development characteristics, the development processing temperature must be increased, but there is a problem that there is a limit to the increase in processing temperature. Bromide ions are removed from the overflow liquid using a separation method such as ion exchange phase 1iN or electrodialysis method.
This led to the idea of making a replenisher.

Journal of the N.M.B.T.E.
urnal of the SMPTE J, )LP
risthoff 65 (1956 edition) 478)
, Bull soc sci photography
c, TAPAN.

Mizusawa 1B (1968 edition 38-44)
However, these bromide ion separation methods also have a number of drawbacks.

For example, in the ion exchange antigreasing method, firstly, the selective removal of bromide ions is low, and a relatively large amount of ion exchange resin is required to remove the bromide ions eluted by development. Secondly, because the selective removal of bromide ions is low, active ingredients other than bromide ions, such as developing agents and alkaline preservatives, combine with the ion exchange resin and are removed, resulting in an economic loss. It is an inviting skewer. Thirdly, the removal rate of bromide ions due to ion exchange phase characteristics decreases continuously when a large amount of developer is processed, and the bromide ion concentration in the developer changes. For this reason, the ion exchange resin must be replaced in a short period of time.Fourthly, for economic reasons, the ion exchange resin must be chemically regenerated through a complicated process and used. Chemicals and waste liquid are discharged.Fifth, the amount of bromide ion removed changes and the bromide ion concentration in the developer solution changes, so the amount of bromide ion separated and removed is determined by continuous chemical analysis of the bromide ion concentration. There are drawbacks such as the need for adjustment.

The advantage is that the process allows the replenisher to contain more than a certain amount of bromide ions, and if it is not necessary to remove all bromide ions, the entire overflow solution can be passed through an ion exchange resin to remove the developing agent. The oxidation products are adsorbed to the resin and removed, and the generation of capri is no longer observed. Therefore, the usual method is to contact all the overflow liquid with an ion exchange resin or to remove the oxidation products with an adsorbent, as reported in the Journal of Applied Photographic Engineering.
plied photography Il:ngi
nering, Vo15.4 (1979 edition) 21
6-219.

As another example, the electrodialysis method consists of a partitioned chamber in which cation exchange membranes and anion exchange membranes are arranged alternately, and electrode chambers (anode and cathode) at both ends. An electrode solution is filled between the ion exchange membranes, and a concentrated solution is filled between every other layer of the ion exchange membrane and circulated. A developing solution is circulated between the layers of the concentrated solution, and electricity is applied to the electrodes to remove the bromide ions accumulated in the developing solution. This is a method in which the anion exchange membrane passes through an anion exchange membrane in the direction of the anode and is removed into a concentrated solution.

This method also has the same drawbacks as the ion exchange resin method. That is, firstly, the selective removal coefficient of bromide ions is small, requiring a long period of dialysis, and in the case of a large amount of overflow liquid, a large electrodialysis tank is required. Second, active ingredients other than bromide ions, such as color developing agents and preservatives,
And alkaline agents are also removed relatively frequently. Third
When dialysis is performed for a certain period of time, ion exchange membranes become clogged with multivalent ions and foreign substances and must be replaced.
It is disadvantageous to process with a developer solution of

Fourth, the dialysis efficiency of bromide ions continuously changes depending on the use of the ion exchange membrane and the salt concentration of the concentrate, so a constant current density and dialysis time do not necessarily remove a constant amount of bromide ions. , the bromide ion concentration must be continuously controlled by analytical operations.

Fifth, unlike the ion-exchange resin method, electrodialysis is very difficult to remove developing agent oxides, so electrodialysis must be performed for a much longer time than the desired time needed to remove bromide ions. There are drawbacks such as not being able to do so.

That is, the disadvantages of these separation methods are that the efficiency of separation and removal of bromide ions is low, and that a large amount of overflow developer must be kept in contact with the separation means for a long time in order to remove the oxidation products of the herbal medicine. In particular, the life of the separation means is shortened and a large amount of expensive developing agent is removed by adsorption or dialysis.

Therefore, an object of the present invention is to provide a development processing method that greatly increases the embryonic properties of ion exchange resins and electrodialysis methods, greatly reduces the consumption of color developing agents, which are active ingredients, and maintains constant development characteristics. The offer is half way.

Furthermore, it is an object of the present inventor to provide a development processing method in which a developing solution can be regenerated and certain development characteristics can be obtained without using chemical analysis.As a result of various studies to achieve the above object, the present inventor has developed a silver halide color photograph. The photosensitive material is heated to a temperature of 35°C or higher and 48°C or lower using a developer containing 4.6 g/l to 3.0 g/l of developer of a phenylenediamine color developing agent having at least one water-soluble group in the amino group. In the method of development processing, the bromide ions of the entire amount of developer that flowed out of the developer tank are removed without removing bromide ions, and the remaining developer that flows out is removed using a separation method, and then The above object is achieved by a color/true development processing method in which both solutions are mixed, a regenerating agent is added to the mixed solution, and the solution is used as a replenisher to keep the bromide ion concentration in the developer substantially constant and maintain the development characteristics. I found out something. That is, when certain color developing agents having a water-soluble group in the amine group are used at a concentration below the concentration of the present invention, the amount of particles removed by ion exchange resin or electrodialysis becomes noticeably smaller, and the development reaction and
It was also found that the amount oxidized by air oxidation was small.

Furthermore, it was found that these color developing agents were not easily oxidized even by high-temperature processing, and it was found that the inactivation of development due to a decrease in the concentration of the developing agent could be compensated for by increasing the temperature, thereby maintaining the development characteristics at a constant level. Ta. Furthermore, it has become clear that even if the bromide ion content is increased to some extent, the temperature can be increased and the development characteristics can be maintained constant. Based on these facts, without removing bromide ions from a part of the oat kuichi 70-liquid by a separation method, the overflow liquid from which bromide ions have been separated by a separation method is mixed, and the missing chemicals other than bromide ions are added to the replenishment solution. I was able to regenerate it and use it as a replenisher to perform development processing.

Conventionally, when using this method, although the bromide ion concentration could be maintained constant, oxides of the color developing agent accumulated, inhibiting development and at the same time causing fog in unexposed areas, especially Capri generation occurs significantly in high-temperature development processing, so all overflow liquid had to be processed using separation means to remove the oxide of the main ingredient and process with a low bromide ion concentration. .

The bromide ion separation method used in the present invention is a conventionally known method, and the method using an ion exchange resin is a treatment using an ion exchange resin that exchanges anions. It is possible to use a resin in which a quaternary ammonium group (strongly basic anion exchange resin) or a primary to tertiary amine group (weakly basic anion exchange resin) is bonded to the molecular substrate as an exchange group. The method is described in British Patent No. 835556 and US Patent No. 325392.
It is detailed in issue 0.

Bromide ion removal by air dialysis is reported in Journal of Applied Photographic Engineering (Journal of Appl.
Photography.

Engineering) Vo15.4.1979
．． The method described on page 208 and Japanese Patent Publication No. 52-34939 can be used.

In the present invention, substantially all of the bromide ions are removed from only a portion of the over-70-liquid by a separation method. The remaining over 7mer fatigue developer which has not been subjected to separation process is mixed with this and a regenerating agent is added to form a replenisher. This allows replenishment containing a constant amount of bromide ions by keeping the volume ratio of the overflow liquid, which is substantially free of bromide ions using the separation method, and the overflow liquid and the regeneration liquid, which do not use the separation method, to be constant. liquid can be obtained, eliminating the need for troublesome chemical quantitative analysis. Furthermore, since the amount of active ingredients removed by the separation method is small and constant, the concentration of these active ingredients in the developer can be kept constant by adding a certain amount of regenerant without chemical analysis.

Since the present invention uses a color developing agent at a lower concentration than conventional ones and contains a relatively high concentration of bromide ions, high-temperature processing is essential in order to maintain development characteristics. The development temperature must be within a range that provides high development activity and hardly decomposes the developing agent, and therefore development is carried out at a temperature of 35°C or higher and 48°C or lower. Particularly preferably, the treatment is carried out at a temperature of 37°C or higher and 43°C or lower.

Since the development temperature is regulated for the reasons mentioned above, the color developing agent concentration and bromide ion concentration are necessarily regulated. The lower the concentration of the color developing agent is, the more difficult it is to remove by separation method and the less likely to cause oxidative decomposition, the lower the concentration, but the lower limit concentration is regulated by the decrease in developing activity, so
．． It is preferable to use 69 or less and 3.0g or more. For the same reason, bromide ion concentration is also present as potassium bromide*&
1/per 1. It is preferable to use Of7 or more and 3.0g or less. The bromide ion concentration is regulated by the ratio of the overflow liquid that does not use the separation method to the total regenerated replenisher. From economical reasons, it is desirable that the proportion of the overflow liquid that does not use the separation method be as large as possible.By using the color developing agent of the present invention and processing within the processing temperature range of the present invention, it is possible to use up to 4 of the total amount of the overflow liquid. I can do it. In order to inhibit development due to a high bromide ion concentration and prevent capriulation due to accumulation of oxides of color developing agents, it is preferable to mix at a concentration higher than or equal to Nagisa or lower.

The color developing agent used in the present invention is a phenylenediamine type color developing agent having at least one hydrophilic group in the amino group, and a typical example of these color developing agents is 4-amino-N-ethyl- N-β-hydroxyethylaniline, 4-amino-3-methyl-N
-ethyl-N-β-methanesulfamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-
Examples include ethyl-N-methoxyethyl-aniline. A particularly desirable color developing agent is 4-amino-N-
Ethyl-N-β-hydroxylaniline and 3-
Methyl-4-aminoly-ethyl-N-β-methanesulfamide ethylaniline is used.

These color developing agents are used in the form of salts such as sulfates, sulfates, and para-toluenesulfonic acid salts.

It is best to add a sequestering agent to the developer.

Generally, when a sequestering agent is added as a preservative to crude drugs, it prevents oxidative decomposition of droxyamine and, as a result, prevents oxidation of the color developing agent. However, not all sequestering agents exhibit sufficient antioxidant activity of the main ingredient. There are currently TS! methods for reactivating overflow fluid into replenishment fluid. Since the liquid is used for a long period of time, it is desirable to use a sequestering agent with high anti-oxidation ability. Particularly in a method such as the present invention, in which all the oxides of the color developing agent are not removed by means of bromide ion separation, extremely high oxidation protection must be provided. The metal ion sequestering system necessary to achieve the object of the present invention includes organic phosphonic acid sequestering systems.

Typical examples of organic phosphonic acid sequestrants that can be desirably used in the present invention include those shown in the following general formulas (I) to (vI).

Ha! Horse is 10o('IM group or -PC+(OM)M group, R
1 is a hydrogen atom or an O8-C4 alkyl group, -(OH
t), 000M group or phenyl group, u is a hydrogen atom,
Lower alkyl group or 1000M group, M is hydrogen cycle, alkali metal atom or ammonium, p is 0 or 1, q
represents an integer from 1 to 4.

[■ko R, x (c+a, posM
,hmm! - is a lower alkyl group, an aryl group, an aralkyl group, a monoalkyl group, or a nitrogen-containing 6-membered ring group. (These groups include -OH, -OR, (R, is a C1-C4 alkyl group, -PO, M-cu, p○8M-N(OH,
PO, M, ), -0OOQ and -N(OH, OOO
M) may have t. NoM represents a hydrogen atom, an alkali metal atom or ammonium.

114, R is a hydrogen atom, a lower alkyl group, or
-11J, group (J is hydrogen atom, -OH group, lower alkyl group, -0,H40H group), bird is hydrogen atom, lower alkyl group, -OH group, -000M group or -ML, group (L is hydrogen Atom, -OH group, -OH, group, -0,H, group, -C,
H40H group, -PO,M, group), atom,
Alkali metal atom, ammonium, hydroxy group, carbonyl group, carboxy group, ether group, biperazo group, morpholif group, hendoze residue, o, N011 alkyl group, alkenyl group, alkylene group, cyclic alkyl group,
carbamoyl group or acyl group, n represents 0 or 1;

[V] 111 R11 is a C8-aCt alkyl group, C8-□ alkoxy, 7 monoalkylamide groups of O+'M*, 0. ~
1. dialkylamine group, amide 7 group, 0. ~1. aryloxy; 4% (represents 4 to 14 arylamino, amyloxy, or benzoyl groups);

Q, ~Q, are -OH groups, C0-2. Alkoxy group, aralkyloxy group, alkoxy group, -0M' group (M'
represents a cation), an amide group, a morpholif group, a cyclic amino group, an alkylamine group, a dialkylamine group, an arylamine group, an alkyloxy group, or a benzoyl group.

81! R1 represents a hydrogen atom or a lower alkyl group, and R□ represents an alkylene amine 7 group.

Horse, NR1. is a hydrogen atom, an alkyl group, -OH group, -o
C! 1H1! l+1 group (n is 1 to 4), -CnH,
nOH group (n: 1-4), -POsM, group, -C!
H, PO, M group, -NR, group (R is a hydrogen atom or an alkyl group) or -N (0HtPO,M, ).

Indicates the group.

In addition to the compounds represented by these general formulas [I] to [vfl, citric acid, glycine, etc. may also be mentioned. However, the compounds represented by the above general formula exhibit even more excellent effects.

Specific examples of the compounds represented by the general formulas [I] to [vIl] include the following.

(1) (2) (3) (4) OH, OH 1 (5) (6) CH:　XOH.

(7) (a) PO, Nag (9) (10) (11) (
12) (xs) (lsu( (17)(18) ku(19J (20)( OH,0OOH (21)(22) OH,0OOH PO,H.

:21S) (2S:2
7) (2B)29) (3o)
(31 npo, H
P.O., H.

I HOoo-OH, H-0-000H (34) (35) (36)
(37) OH, OH Soy CHl PO, H.

0 (41) OK
0H (42) 1 HOCH! 0H(OH)-0H,0-P-(ONa)t
1 HO-OH, -0TI-OH, 0-P-(011)*(
46) 1 HOOH, 0-0)! t-0-P-(0H)1-1 (47) (48) (5 ri
(52)NH.

(53) Oh.

(54) (56) (5?) (5B) (59
) OHOH (6Q) NaO0Na (6υ 0 0 (62) 0 0H0H (63) 0 (6li (65)Hs (68) 1 OHOH ('IH, etc., in addition to triethanolamine, hydroxyethyliminodiacetic acid, Diethyltriaminepentaacetic acid and dihydroxyethyliminoacetic acid can be used.

As the most preferred metal ion sealant in the present invention 1-hydroxyethylidene-1,1-niphosphonic acid P.O., H.

0Ha-0-011 po, ii.

Examples include hydroxyethyliminodiacetic acid. It is particularly preferable to use these two metal ions in combination.

These metal ion sequestering agents are used in an amount ranging from 0.01 to 1009 per 11 parts of the developer solution, particularly preferably from 0.059 to 1009 per 11 parts.
Used in the range of 0g.

The regenerating agent of the present invention is one that activates a fatigued developer, and commonly known agents such as ordinary color developing agents and water are used.

The regenerating agent used in the present invention is added to the overflow liquid treated using a separation method and the overflow liquid treated without a separation method, respectively, or a mixture thereof, and is used to correct the overflow liquid to the selected replenisher concentration. used. In addition, the developing solution is carried out by the photosensitive material and decreases, so even if you add the missing chemicals to only the overflow solution and regenerate it as replenisher, the amount of replenisher gradually decreases, so it is necessary to add new replenisher. Yes, and the regenerant usually contains chemicals equivalent to this new replenisher.

Therefore, the regenerant includes the supply of only water.

The regenerating agent and color developing agent used in the present invention may contain known developer components in addition to the above components. As the alkaline agent, buffering agent, etc., sodium hydroxide, sodium carbonate, potassium metaphosate, or borax may be added singly or in combination. In addition, due to pharmaceutical needs or for the purpose of increasing ionic strength, disodium hydrogen phosphate,
Various salts such as sodium bicarbonate, horic acid, etc. can also be used.

If necessary, it is also possible to add inorganic or organic anti-capri agents, and typical examples of these compounds include inorganic halide compounds such as potassium bromide and carlyrum iodide, as well as U.S. Pat. 6-nitrobenzimidazole described in No. 496,940, No. 2,497,
5-nitropenzimidazole described in No. 917 and No. 2,656,271, as well as 0-7 enylenediamine, mercaptobenzimidazole, mercaptobenzoxazole, thiouracil, 5
-Methylbenztrizole, or Special Publication No. 1986-41
Examples include the heterocyclic compounds described in Japanese Patent No. 675.

In addition to these various ingredients, there are also
Publication No. 45-6149, U.S. Patent No. 3,295,9
The development inhibitor disclosed in No. 76 and, if necessary, a development accelerator may also be added. Among these development accelerators are U.S. Pat.
Various pyridium compounds typified by Patent Publication No. 1,247 and Japanese Patent Publication No. 44-9503, other karaonic compounds, cationic color pigments such as phenosafranine, neutral salts such as talic nitrate A, and U.S. patents. No. 2,533
, No. 990, No. 2,531,832, No. 2,95
Nonionic compounds such as polyethylene glycols and derivatives thereof, polythioether slopes, etc. described in the specifications of No. 0,9 FuO, No. 2,577,127, and Japanese Patent Publication No. 44-9504; The organic solvents and organic amines described in the above publication include ethanolamine, ethylenediamine, jetanolamine, triethanolamine, and the like. In addition, benzyl alcohol, phenethyl alcohol, which are described in U.S. Pat. It is an accelerator.

In addition, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide,
Other compounds described in Japanese Patent Publication Nos. 47-33378 and 44-9509 can be used as solvents for increasing the solubility of the developing agent.

In the color developer according to the invention, an auxiliary developer can also be used together with the developing agent. These auxiliary developers include, for example, N-methyl-P-aminophenol hemisulfate (metholn, phenidone, M, x-
Diethyl-P-amino-yz no#*ai! salt, N,
N, N', N'-f)? Methyl-P-phenylenediamine tong! ! Salts and the like are known, and the preferred additive thereof is usually 0.02 g to 1.09/l. In addition, competitive couplers, fogging agents, color couplers, and development inhibitor-releasing couplers (so-called DI
R coupler] or a development inhibitor-releasing compound may be added.

In the present invention, it is most desirable that the development treatment step be the first step. In such embodiments, the developing solution is carried away by the photographic material being processed, reducing the amount of halogen ions accumulated. For the same reason, it is also preferable that the pretreatment for the development process is a water washing process.

In the present invention, a fatigued developer and/or over 7p
- The regenerating agent added to the regenerated portion of the solution can include all agents known to be added to color developing solutions. These drugs may be added in either powder or liquid form.
Further, if necessary, it can be added after being dissolved in water.

Additionally, water may be added to prevent thickening due to evaporation and to reduce the accumulation of halogen ions.

In special cases, bromide ions can also be added.

When applying the method of the present invention, it is preferable to suppress development by increasing the processing temperature, but it is also possible to add a development accelerator.

As development accelerators particularly effectively used in the present invention, thioether compounds (for example, U.S. Pat. No. 3,201,24
No. 2, No. 3,046,129, No. 3,630,7
Examples include those described in each specification of No. 30 and thiogentanol. ), lower ketones (e.g. acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, cyclopentanone, etc.), lower oximes (e.g. acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, etc.), polyethylene glyfur with an average molecular weight of 400 to 6000, and polyethylene Glycol derivatives (e.g., U.S. Pat. No. 2,531,832;
950.9 'i' No. 0, Specifications of No. 3,996,054, Japanese Patent Publication No. 44-9504, No. 49-3378
No. 8, Japanese Patent Application Publication No. 51. ．． No. 142328, No. 49-691
No. 24, No. 50-81539, No. 52-108130
Examples include those described in the specifications and gazettes.

The present invention will be described in detail below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example-1 A color developing solution containing each of the color developing agents shown in Table-1 was prepared and divided into three equal parts (a), (b) and ((1), each of which was further divided into six equal parts, (a -1,' ) or a-6), (b-
1) or b-6) and (0-1) or 0-.

The developers of groups a and b were stored at 38° C. in a 11 glass beaker for 3 weeks. For water evaporation during storage, pure water was added to compensate for evaporation so that the original liquid ff1ll was always maintained.

After storage, color developer (a-Yufu or A-6) 11 and strong basic ion exchange resin (trade name Amber 5 I) I
The ion exchange resin was mixed with RA400, ROHM Co., Ltd., and Nzam/manufactured by Tendo Hearth Co., Ltd., and treated for 1 hour and 40 minutes, followed by separation of the ion exchange resin. The potassium bromide concentration in the f solution was determined by silver nitrate titration, and the concentration before treatment with the ion exchange resin was 1.311/
I added the missing amount to make it 1.

400 m of each of 11 of the color developing solutions (b-1) to b-6) after storage was taken and mixed with 1 om/ml of the above-mentioned strong basic ion exchange resin and treated for 1 hour and 40 minutes. After processing, separate the ion exchange resin into P, and add the remaining color developer to the F solution.
ml and set the potassium bromide concentration as above,
The deficiency was corrected to 13 g/l. The color developer (C21) or 0-6) is used for development processing.
A sealed bottle was filled with nitrogen and stored at 5°C until use.

Processed Sakura color paper (manufactured by Konishi Rokusha Co., Ltd., K.) was used, and stepwise exposure was applied using a light cutter in a conventional manner, and the following processing was carried out.

Processing process Color development 38℃ 3'30"2, bleach fixing 33℃ 1'30"3, washing with water 33℃ 3'4, drying
70°C The composition of the color developing solution used in the experiment is as follows.

The following bleach-fix solution was used.

Ethylenediaminetetraacetic acid disodium salt 5
Ii-engineered ethylenediaminetetraacetic acid iron plate complex salt replacement salt 5
0 g anhydrous silium sulfite 10 g ammonium thiosulfate 70% aqueous solution 160 g water 11
Then, the pH was adjusted to 7.2 with potassium carbonate.

Table-1 Color developer obtained by processing using color developer (a-1) or &-6), (b-1) or b-6) and (C-1,) or 0-6) The maximum and minimum concentrations of the sample
DA-6 type densitometer (Kotoroku Photo Industry, 11:,
As can be seen from the results in Table 2, the reflection density was measured using a standard treatment (0-1).
) or 0-6), a color developing solution (a-1) or a-2 using a color developing agent treated outside the present invention
), (in the case of total ion-exchange resin treatment, the 2 maximum concentration is greatly reduced and the minimum concentration is also slightly higher, and when the amount of developer is treated with ion-exchange resin (b-1) or b-2) However, the minimum concentration is extremely high and the maximum concentration is also somewhat low, making it impossible to put it to practical use. In (a-3) or a-4), in which the color developing agent of the present invention is used at a concentration higher than the concentration range of the present invention, and the entire amount of the developer is treated with an ion exchange resin, the minimum concentration is high and the maximum concentration is low. In addition, even if the wooden structure of the developer is treated with an ion exchange resin (b-3) or b-4), a desired maximum density can be obtained, but the minimum density is high and poses a problem in practical use. (a-5) or a used within the concentration range of the present invention and treated with ion exchange resin
-6), the lowest concentration is desirable but the highest concentration is low; on the other hand, 4il was treated with ion exchange resin (b-52 or 1).
3-6), both the lowest and highest concentrations were treated as standard (0-
It can be seen that desirable values close to 1) or 0-6) can be obtained. That is, when the color developing agent according to the present invention is used at the concentration according to the present invention, in the regeneration method in which bromide ions are removed using an ion exchange resin, in order to efficiently use the ion exchange resin, the color developing agent is used. Even if only a portion of the solution is treated with an ion exchange resin in order to remove the required amount of bromide ions from the solution and mixed with the remaining color developing solution, the processing can be carried out without destroying the photographic performance. This enabled economically advantageous processing without loss of color developing agent.

Example 2 Color developer 11 for color negatives with a sodium bromide content of 163 g was mixed with a strongly basic ion exchange resin (if the same as in Example 1 was used) according to Table 3, and after processing for 1 hour and 40 minutes, the ion exchange resin was mixed. was separated by f.

The concentration of the color developing agent in the KBr in the color developer treated with the ion exchange resin and in the developer mixed with the color developer and the untreated color developer was determined and shown in Table 4.The color developer used was as follows. The color photosensitive material to be processed used was the same as in Example 1.

1) Adjusting H with KOH 10.20 Table 3 Bromide ions were determined by silver nitrate titration, and color developing agents were determined by cerium titration.

The results are shown in Table-5.

Table 5 As can be seen from Table 3, bromide ions were not completely removed in Comparative Examples 2-1 and 2-2, and bromide had to be quantified and corrected to the desired bromide ion concentration after each regeneration treatment. This is extremely complicated and results in a large loss of color developing agent. In Comparative Example 2-3, bromide ions are completely removed, but the bromide ion concentration of the developer mixed with the untreated ion exchange resin solution is not much different from that of the developer before treatment, and there is no substantial effect.

In Comparative Example 2-4.2-2, bromide ions are completely removed by increasing the amount of ion exchange resin, but this method results in a greater loss of color developing agent, resulting in a greater economic loss.

On the other hand, in the treatments 2-4 to 2-6 according to the present invention, bromide ions can be removed substantially completely, so that the desired bromide concentration in the replenisher can be automatically adjusted by adjusting the mixing ratio of the ion exchange treated liquid and the untreated liquid. can be determined. It is also found that these treatments can reduce the loss of color developing agent. In such processing, photographic performance can be maintained at a constant level by simply adding a pre-mixed treatment containing a certain amount of color developing agent when regenerating the overflow solution into replenisher, and analytical operations can be carried out to determine component decay. It can be made unnecessary.

The results in Table 5 also show that as the proportion of the developer treated with the ion exchange resin used as the separation means decreases (the concentration of the main agent decreases), the adsorption of the main agent to the resin also decreases.

Example-3 The color developing agent of the color developer of Example-2 was 4-amino-
The same treatment as in Example 2 was carried out in place of 3-methyl-N,N-diethyl diline sulfate. Table 6 shows the results of quantifying the color developing agent after mixing a developer using a separation method using an ion exchange resin and a developer using no separation method.
Shown below.

Table 6 As can be seen from the results in Table 6, compared to the results in Table 5, the adsorption amount of the active agent is larger in the case of active agents that do not have water-soluble groups in the 7 groups, and the ratio of separation treatment using resin is Even if the amount is lowered, it is not possible to significantly prevent the loss of crude drugs. Furthermore, unlike the developing agent according to the present invention, such a main agent shows that the amount of adsorption does not decrease even if the concentration decreases.

Example 4 1.50 g of potassium bromide color developer solution 501 was mixed with a monovalent ion selectively permeable ion exchange membrane (Asahi Glass ■).
Electrodialysis was performed at a current of 0.2 ANW and a pressure of 6 to 8 V using an electrodialysis apparatus using a Selemion ion exchange membrane.

The flow rate of developer to the dialysis tank is 4j! /min, 14
Time dialysis was performed as a comparative example.

Table 7 shows the concentration of each component after dialysis.

The current @! The composition of Ei is shown below.

pH 10, 20 On the other hand, as the treatment method of the present invention, the same method as in Example 3 was used, and the fJl and gI solutions were 5 (1/jllJ, of which 25
1 was subjected to electrodialysis under the same conditions as Example 3. The dialysis time was 10 hours, and a developer without dialysis was added to the developer after dialysis and mixed. Table 7 shows the degree of each component at that time.

For reference, the desired concentration of the replenisher when regenerating the developer and obtaining the replenisher is also shown in Table 7.

As can be seen from the results in Table 7), bromide ions are completely removed by the method of the present invention even when electrodialysis is used as the separation method, and the desired concentration of bromide ions in the replenisher can be determined by the separation method. It can be easily determined from the mixing ratio of the liquid used and the liquid not used. In addition, the loss of the main drug is small, and the loss of other components can be reduced as well.

Furthermore, since the life of a dialysis membrane corresponds to the dialysis time, the present invention can extend the membrane life by about 30%.

EXAMPLE Using Sakura Paper (manufactured by Konishiroku Photo Industry Co., Ltd.), stepwise exposure was applied using a light pattern in a conventional manner, and then processing was carried out in accordance with the following sequence.

Treatment process color development m @ 33IlCA/46℃ 3 minutes 3
0 second bleach fixing 33″C 1 minute 30 seconds Washing 30℃ 2 parts Drying 75℃~85℃
45 seconds total 7 minutes 45 seconds Color developer (mother liquor) Fluorescent brightener (Shin Nisso Kako, Keikoru PK-Conc) 1
．． 0g Benzyl Alcohol 13.0d Ethylene Glyfur 13.0Id Potassium Sulfite 2I Human O-xylamine Sulfate: 3.5! ? charcoal potassium
2.6g polyethylene glycol
3g magnesium chloride
0.3g 1-hydroxyethylidene 1,1-diphosphonic acid 0.6g 4-amino-3-methyl-N-ethyl-N
-(β-methanesulfonamidoethylnoaniline sesquisulfate.

monohydra)'
4.29 pH was adjusted to 10.20 This developer solution was divided into four parts, and potassium bromide was added to the developer solution (A) or 2) as follows.

Developer (A), KBr o, e+l
l/1# (B) KEr 1.3
9/IJF (0) KBr 2.
Og/IJF (D) KBr 3
．． The Og/l bleach-fix solution color development process was carried out in a preliminary test in which each of the color developers (A) to D) was varied from 33 DEG C. to 46 DEG C. in 1 DEG C increments and processed for 14 steps for 3 minutes and 30 seconds. As a result, the color developer (A) was
The processing temperatures that resulted in almost the same concentration as the standard second processing were selected and are shown in Table 8. The processing temperature of each developer is the color developer (B
), the temperature was 38°C, and the temperature was 40°C for the color developer ((1), and 46°C for the color developer (DI). The highest and lowest densities (reflection density) obtained for each are shown. -8.

Table 8 As can be seen from Table 8, even if the concentration of potassium bromide was increased, no increase in fog was observed due to the small adjustment of the processing temperature, and no decrease in the maximum concentration was observed. In some cases, the bromide ion concentration in the replenisher is low because the solution does not contain bromide ions, or a developing solution that does not remove bromide ions using a very small amount of bromide separation method is used directly as part of the replenisher. inevitably increases. However, according to the method of the present invention, photographic performance can be maintained even if the bromide ions in the replenisher or tank solution increase by adjusting the physical conditions such as the processing temperature as in this example and the chemical conditions such as the use of a development accelerator.

That is, by the method of the present invention (1) The amount of chemicals added to the regenerant can be reduced.

(2) The amount of ion exchange resin used can be reduced, and the regeneration tendency of the resin is reduced, so the amount of waste liquid due to resin regeneration is reduced.

(3) Membrane lifetime is increased when electrodialysis is used as the separation method.

(4) No analysis operation is required.

(5) Manpower for developer regeneration can be saved.

etc., and other great effects are exhibited.

The economic and environmental pollution prevention effects brought about by this are extremely large.

Agent Kanmi Kuwa Hara

Claims (1)

[Scope of Claims] 1) A silver halide color photographic light-sensitive material comprising at least one
114.6 g to 3.0 g of a phenylenediamine color developing agent having 7 water-soluble groups in 7 mino groups per 11 days of developer solution. Using fJil image solution containing OI gold at 35°C or higher 48
In the method of developing at temperatures below ℃, the name of the total amount of developer that flows out from the developer tank! o), the bromide ions are not removed from the remaining developing solution that flows out using a separation method, and then the two solutions are mixed and a regenerating agent is added to the mixed solution to make a replenisher. A developer processing method characterized by keeping lfV (bromide ions) in a developer present in a developer tank substantially constant and maintaining development characteristics. 2) The developer contains -(0H1)nOH as a water-soluble group. The developing solution processing method according to item 1 of the patent scope, characterized in that it contains a paraphenylenediamine color developing agent in which -C,H4NH30,OH, group is substituted with an amino group. 3) The post-development treatment method according to Patent Application Section 1 or 2, characterized in that the developer solution contains bromide ions in an amount of at least 0.3 g per 11 potassium bromide ions. 4) Bromide ions in the developer present in the developer tank are 19/l to 3g as potassium bromide per 11 of the developer.
5) A method for processing a developer according to claim 1, 2 or 3, characterized in that: Claims 1 and 2
The developer processing method according to item 3, item 4, or item 4. (2) A developer processing method according to claim 1, 2, 3, 4f, or #>5, characterized in that the developer contains an organic phosphonate metal ion sequestering agent. .