JPH06202292A - Solution and method for replenishment for bleaching and fixing solution - Google Patents

Abstract

PURPOSE: To produce a replenishing liq. for bleaching-fixing liq., capable of executing a replenishing in a state in which an ammonium ion content is either low or absent and with a very low flow rate in a method and composition for replenishing a bleaching-fixing liq. CONSTITUTION: The replenishing liq. for bleaching-fixing liq. is constituted by incorporating separately independent components A, B and C, and thiosulfate and a preserving agent are incorporated in the component A; aminopolycarboxylic acid ferric iron complex is incorporated in the component B; acid is incorporated in the component C; and the liq. is constituted, so that the total content of an ammonium ion of the component A, B and C is lower than 50mol.% of the total cations.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to the processing of silver halide photographic materials. More specifically, the present invention relates to methods and compositions for replenishing bleach-fix solutions.

[0002]

2. Description of the Related Art A silver halide light-sensitive material whose main silver halide component is silver chloride is usually processed by color-developing and bleach-fixing the material. Bleach-
The fixing solution is usually a ferric complex salt of an organic chelating compound,
It contains, for example, ethylenediaminetetraacetic acid (EDTA) and a fixing agent such as thiosulfate.

As environmental concerns become more and more important, it is desirable to remove unwanted chemicals from photographic processing solutions such as ammonia and ammonium salts.
Efforts have been made in the processing procedure described above to replenish the bleach-fixer at low flow rates in order to minimize the effluent discharged into the sewer. Currently, the replenishment rate is 53.8
All bleach-fix solutions, which are ml / m ² , use ammonium thiosulfate as fixative. Attempts to remove or reduce this ammonia by displacing it with different monovalent cations while maintaining a low replenishment rate have been demonstrated by the solubility of non-ammonia systems containing ferric salts of organic chelating agents and fixing agents. Is always failing because of low.

US Pat. No. 4,954,426 discloses a low replenishment rate bleach in which more than 80 mol% of all non-metallic cations present in the fixer-bleach replenisher are ammonium ions. The fixer is discussed. U.S. Pat. No. 3,706,561 describes low ammonia bleach-fix solutions having higher pH values to avoid solubility problems. The use of higher pH values delays the bleaching, which necessitates the use of a second ligand.

Until recently, bleach-fix replenishers have been one-component solutions. Kodak's bleach-fix solution, Kodak Ektacolor RA Bleach-Fix D-Rep, which has an effective replenishment rate of 19.4 ml / m ² , is a three component replenisher. This system, however, uses ammonium thiosulfate as a fixing component. JP-A-55
-79446 discusses the use of a two component replenishment system to achieve low replenishment rates. With this system, a 90 second bleach-fix was used, and the pH of the bleach-fix was always maintained above 7.0,
As a result, as mentioned above, insufficient bleaching is obtained.

US Pat. No. 5,055,382 describes a three component bleach liquor regeneration kit. However, its first component is an alkaline solution containing a buffer and an aminopolycarboxylic acid, which is added to the depleting bleach-fix solution prior to electrolytically recovering silver from the solution. The other two components are
It contains iron salts and thiosulfates and these components are also added to the depleting bleach-fix solution.

[0007]

The problem to be solved by the present invention is a replenisher for a bleach-fix solution which has a low or absent ammonium ion content and is very low. It is to provide a replenisher solution that can be replenished at a flow rate. This replenisher is capable of rapidly bleaching-fixing photographic elements and having a pH value below 6.5 to maintain adequate bleaching capacity.
It must be possible to maintain the fixing bath.

[0008]

SUMMARY OF THE INVENTION The present invention is a replenisher for a bleach-fix bath, which comprises separate and independent components A, B and C, wherein component A is a thiosulfate salt. And a preservative, component B contains an aminopolycarboxylic acid ferric complex, component C contains an acid, and components A and B
To provide a bleach-fix replenisher solution characterized by a total ammonium ion content of less than 50 mol% of all cations. In one embodiment, the thiosulfate salt comprises sodium or potassium thiosulfate and the ferric aminopolycarboxylic acid complex comprises ferric aminopolycarboxylic acid sodium or ferric potassium complex.

The present invention further comprises adding a replenisher as described above to the bleach-fix solution while maintaining the pH value of the bleach-fix solution between 5.5 and 6.5. And a method of replenishing the bleach-fixing solution. The present invention is also a method of bleaching and fixing a photographic element in a bleach-fix solution for 45 seconds or less, wherein the bleach-fix solution is replenished with the replenisher solution described above, and the pH of the bleach-fix solution.
It provides a way to keep the value between 5.5 and 6.5. In one embodiment of this method, the photographic element has a silver chloride content of greater than 90 mol% and a silver content of less than 0.86 g / m ² .

The three component replenishment system of the present invention provides a replenisher that is stable at low ammonia or non-ammonium components at high concentrations. The ammonium thiosulfate can be wholly or partially replaced by sodium or potassium thiosulfate in the bleach-fix composition. The ferric ammonium aminopolycarboxylate can also be replaced with potassium or sodium aminopolycarboxylate if it is desired to do so. In this way it is possible to remove or reduce ammonia in the bleach-fix bath while maintaining a replenishment rate of less than 27 ml / m ² . This also makes it possible to prepare bleach-fix solutions which work at pH values below 6.5 and which require processing times of no more than 45 seconds.

[0011]

The replenisher of the present invention consists of three separate and independent components. Component A contains a thiosulfate salt and a preservative, component B contains a ferric aminopolycarboxylate, and component C contains an acid. The thiosulfate can be an alkali metal salt of thiosulfate, sodium or potassium thiosulfate being preferred. This salt may also be a combination of alkali metal thiosulfate and ammonium thiosulfate. If ammonium thiosulfate is used, mol% ammonium cations contained in components A and B
Must be less than 50 mol% of all cations present. Preferably, the thiosulfate is free of any ammonium ion.

The concentration of thiosulfate is about 0.75 mol / l.
To about 5.0 mol / l, 2.0 mol / l
˜3.0 mol / l is preferred. Also, component A should contain a preservative. A preferred preservative is sulfite, some examples of which include sodium sulfite, sodium metabisulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, ammonium bisulfite, potassium metabisulfite, and formaldehyde bicarbonate. Examples include sodium sulfite. The amount of preservative can be from 0.05 mol / l to 1.0 mol / l, with 0.45 mol / l to 0.55 mol / l being advantageous. Also, a mixture of preservatives may be used. Also,
Component A may contain other additives, such as bleach accelerators, fixing accelerators, free ligands, and buffers, among others. The pH value of component A can be 4-10.

The aminopolycarboxylic acid of the ferric aminopolycarboxylic acid complex in component B can be any such acid which is useful in bleaching silver halide emulsions. Examples of useful aminopolycarboxylic acids include, but are not limited to, the following: A-1: diethylenetriaminepentaacetic acid A-2: diethylenetriaminepentaacetic acid pentasodium A- 3: Ethylenediamine-N- (2, hydroxyethyl) -N, N ', N'-triacetic acid A-4: Ethylenediamine-N- (2, hydroxyethyl) -N, N', N'-triacetic acid trisodium salt A-5: Ethylenediamine-N- (2, hydroxyethyl) -N, N ', N'-triammonium triacetate A-6: 1,2-diaminopropanetetraacetic acid A-7: 1,2-diaminopropanetetra Disodium acetate A-8: Nitrilotriacetic acid A-9: Sodium nitrilotriacetic acid A-10: Cyclohexanediaminetetraacetic acid A-11: Cyclohexanediaminetetraacetic acid Thorium A-12: N-methyliminodiacetic acid A-13: Iminodiacetic acid A-14: Dihydroxyethylglycine A-15: Ethylenebis (oxyethylnitrilo) tetraacetic acid A-16: Ethylenediaminetetrapropionic acid A-17: 1 , 3-diaminepropanetetraacetic acid A-18: ethylenediaminetetraacetic acid A-19: 1,2-propylenediaminetetraacetic acid or an alkali metal salt or ammonium salt thereof A-20: triethylenetetramine hexaacetic acid or an alkali salt or ammonium salt thereof A-21: 1,4-Diaminobutanetetraacetic acid or its alkali salt or ammonium salt A-22: 2-Propanoldiaminetetraacetic acid or its alkali salt or ammonium salt A-23: 1,3-Butylenediaminetetraacetic acid or its salt Alkaline salt or ammoni Umium salt A preferred aminopolycarboxylic acid is ethylenediaminetetraacetic acid (EDTA).

The ferric aminopolycarboxylic acid complex can be a ferric ammonium aminopolycarboxylic acid complex or a complex with an alkali metal such as sodium or potassium. This complex may also be a mixture of those mentioned above. The concentration of the ferric aminopolycarboxylic acid complex is from about 0.05 mol / l to about 2.
Should be up to 0 mol / l, from 1.25 mol / l
1.75 mol / l is preferred. In addition, component B can contain various additives, such as excess ligand and buffer. The pH value of this solution can be between 3 and 10.

The third component, component C, is an acid. The acid must be stable for use in photographic processing solutions. The pH value of component C is such that the low replenishment rate is maintained while the pH value of the bleach-fix solution is pH = 5.5-6.
It should be as retained in 5. Examples of suitable acids may be acetic acid, propionic acid, citric acid or succinic acid, sulphonic acid, and nitric acid. Acetic acid is preferred. It is this independent acid component that enables the low replenishment rate of the replenisher of the present invention. Since the other components are not required to have low pH values, the concentrations of thiosulfate and ferric aminopolycarboxylic acid complex are
It can be higher without compromising solubility.

The respective components of the replenisher solution should be added directly to the bleach-fix solution without being premixed or diluted. One of the objects of the present invention is to provide a replenisher having the lowest possible replenishment rate while still retaining a stable and effective bleach-fix and replenisher. The total amount of replenisher that must be added to the bleach-fix bath depends on the type of cations in components A and B and the amount of carryover from the preceding solution. here,
Carryover refers to the amount of liquid per square unit carried by the photographic element from the preceding bath into the bleach-fix solution. The preceding baths are several different baths,
For example, it can be any one of a developing bath, a stop bath and a washing bath. The present invention is most useful when the preceding bath is alkaline.

When the alkali metal thiosulfate is used with a ferric ammonium polycarboxylate complex, the amount of replenisher used per square unit of photographic material to be processed is:
Approximately 0.5 to 1 times the carryover from the preceding solution. For example, if the carryover is 43 ml / m ² , 2 per square meter of photographic element processed.
1.5-43 ml of replenisher should be added. The preferred ratio of component A / component B / component C is about 3/1/1, based on the total amount of replenisher added.

When an alkali metal thiosulfate is used with a potassium ferric polycarboxylate complex, the amount of replenisher used per square unit of photographic material to be processed is about 0 of carryover from the preceding solution. .625-1.2
5 times. Therefore, if the carryover is 43 ml /
If it is m ² , then about 26.9 to 53.8 ml of replenisher should be added per square meter of film processed. Component A / Component B with respect to the total amount of replenisher added
A preferred ratio of / component C is about 3/1/1.

When an alkali metal thiosulfate is used with a sodium ferric polycarboxylate complex, the amount of replenisher used per square unit of photographic material processed is about 2 times the carryover from the preceding solution. 0.5 to 5 times. Therefore, if the carryover is 43 ml / m ² , 10 per square meter of film processed.
7.5-215 ml of replenisher should be added. The preferred ratio of component A / component B / component C is about 3/6/1, based on the total amount of replenisher added.

If the amount of ammonium cations in each component increases, the amount of solution used in that component of the replenisher will decrease. Using the guidelines provided above, one of ordinary skill in the art will be able to determine the optimal amount of replenisher solution that can be utilized in various replenisher composition. By utilizing the replenisher of the present invention, the bleach-fix solution to be replenished can be maintained at a pH value of 5.5 to 6.5, and the working concentration of the bleach-fix solution is as follows. Can be retained: thiosulfate 0.05 mol /
1 to 1.0 mol / l, preservative 0.01 mol / l to 0.5
Mol / l, and aminopolycarboxylic acid ferric iron complex 0.
025 mol / l to 0.25 mol / l; thiosulfate 0.4
Mol / l to 0.65 mol / l, preservative 0.075 mol / l
Preference is given to 1 to 0.2 mol / l, and aminopolycarboxylic acid ferric complex 0.025 mol / l to 0.2 mol / l. This allows a bleach-fix time of 45 seconds or less.

The photographic element to be processed can contain any of the conventional silver halide as a light-sensitive material, for example, silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide. ,
And the mixture can be mentioned. However, preferably the photographic element is a high chloride element and comprises at least 9
It contains 0 mole percent silver chloride. The most useful photographic elements in this invention have a silver content of 0.86 g.
/ M ^{2 or} less.

The photographic elements can be single color elements or multicolor elements. Multicolor elements usually contain dye image-forming units sensitive to each of the three primary colors in the visible spectrum. Each unit can consist of a single emulsion layer or else multiple emulsion layers sensitive to a given spectral region. The layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art. In another form, the emulsions sensitive to each of the three primary regions of the spectrum are provided as a single segmented layer, eg, US Pat. No. 4,362,806 issued Dec. 7, 1982. (Whi
It can be arranged by using fine containment cells as described in tmore). The element can contain additional layers such as filter layers, interlayers, overcoat layers, subbing layers and the like.

Suitable materials for use in the emulsions and elements of the invention are described below, in which Research Disclosure (Research Disc).
Loss), December 1989, Item 308.
119, United Kingdom, Hants P010 7DD, Emsw
orth, North Street 8, TheOl
dust from Harbourmaster's
rial Opportunities Ltd. Published,
Will refer to. This publication will be referred to hereinafter as "Research Disclosure."

The silver halide emulsions used in the elements of this invention can be either negative or positive working. Research on suitable emulsions and their preparation
Disclosure, Sections I and II, and the publications cited therein. Some of the suitable vehicles for the emulsion layers and other layers of the elements of this invention are described in Research Disclosure, Section IX, and the publications cited therein.

The silver halide emulsion can be chemically and spectrally sensitized by various methods. An example of the method is as follows.
Research Disclosure Sections III and IV
It is described in. Elements of the invention include Research Disclosure, Section VII, paragraphs D, E, F.
And G, and various couplers as described in the publications cited therein, but are not limited to those couplers. These couplers can be incorporated into elements or emulsions as described in Research Disclosure Section VII, paragraph C, and the publications cited therein.

The photographic elements of the present invention or individual layers thereof include, among other things, brighteners (research disclosure, exemplified in Section V), antifoggants and stabilizers (research disclosure, exemplified in Section VI), antifouling agents and Image dye stabilizers (Research Disclosure, Section VII, exemplified in paragraphs I and J), Light Absorbing and Scattering Substances (Research Disclosure, Section VIII), Hardeners (Research Disclosure, Section X), plasticizers and Lubricants (Research Disclosure, exemplified in Section XII), Antistatic Agents (Research Disclosure, exemplified in Section XIII), Matting Agents (Research Disclosure, exemplified in Section XVI), and Development Adjusters (Research Disclosure, Secular). Action XXI
Can be included).

The photographic elements can be coated on a variety of supports including, but not limited to, those described in Research Disclosure, Section XVII, and the publications cited therein. Not a thing. The photographic elements are exposed to actinic radiation, usually in the visible region of the spectrum, to form a magnetic image, as described in Research Disclosure, Section XVIII, which is then transferred to Research Disclosure, Section XIX. It can be processed as illustrated to form a visible dye image. Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. The oxidized color developing agent further reacts with the coupler to form a dye.

The color developing solution usually contains a primary aromatic amino color developing agent. These color developing agents are known and widely used in various color processing processes. These color developers include aminophenols and p-phenylenediamines. Particularly preferred are 4-amino-3-methyl-N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-β- (methylenesulfonamido) ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N-β-hydroethylaniline sulfate, 4-amino-
3-β- (methanesulfonamido) ethyl-N, N-diethylaniline hydrochloride, and 4-amino-N-ethyl-N- (2-methoxyethyl) m-toluidine di-p-toluenesulfonate.

Examples of aminophenol developers are o-aminophenol, p-aminophenol, 5-amino-2.
-Hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-dimethylbenzene and others. Particularly useful primary aromatic amino color developers are p-phenylenediamines, and especially N, N-dialkyl-p-phenylenediamines, where the alkyl or aromatic groups may be substituted or unsubstituted. . Examples of useful p-phenylenediamine color developers include: N, N-
Diethyl-p-phenylenediamine monohydrochloride, 4-N,
N-diethyl-2-methylphenylenediamine monohydrochloride, 4- (N-ethyl-N-2-methanesulfonylaminoethyl) -2-methylphenylenediamine sesquisulfate monohydrate, 4- (N-ethyl- N-2-hydroxyethyl) -2-methylphenylenediamine sulfate, 4-
N, N-diethyl-2,2'-methanesulfonylaminoethylphenylenediamine hydrochloride, etc.

The color developing solution usually contains a primary aromatic amino color developing agent and various other agents such as pH.
Alkali, bromide, iodide, benzyl alcohol, antioxidant, antifoggant, solubilizer for adjusting the value,
Contains whitening agents. The photographic composition for color development is 7
And most commonly used in the form of an aqueous alkaline use solution having a pH value in the range of about 9 to about 13. These compositions contain one or more of the well known and widely used pH buffers to provide the required pH values, such as alkali metal carbonates or phosphates. Potassium carbonate is particularly useful as a pH buffering agent for color developing compositions.

When a negative type silver halide emulsion is used, a negative image is obtained by the above-mentioned processing steps. To obtain a positive (or reversal) image, this step is performed by development with a non-chromogenic developer to develop the exposed silver halide rather than dye formation, and then the element is developed. The unexposed silver halide can be developed so that it can be developed by uniform fogging. Otherwise, a direct positive emulsion can be used to obtain a positive image.

Development is followed by the conventional steps of bleach-fixing, washing, and drying to remove silver and silver halide. In general, a separate pH reducing solution called a stop bath is used to terminate development prior to performing bleaching. Stabilizer baths are commonly used to perform the final washing and hardening of the photographic element after bleaching and fixing prior to drying. Common techniques for processing are:
See Research Disclosure, Section XIX.

Preferred processing procedures for color photographic elements, especially color negative films and color photographic papers, include: (P-1) Color development / stop / bleach-fix / wash / stabilize / dry. P-2) Color development / stop / bleach-fix / stabilize / dry (P-3) Color develop / bleach-fix / wash / stabilize / dry (P-4) Color develop / bleach-fix / wash (P-4) -5) Color development / bleach-fixing / stabilizing / drying (P-6) Color developing / stopping / washing / bleaching-fixing / washing /
In each of the drying processes (P-1) to (P-6),
You can think of various changes. For example, a bath such as a pre-hardening bath can be used prior to color development, or a stabilizing step may be followed by a washing step. Furthermore, a reversal process is conceivable in which the additional steps of black and white development, chemical fog bath, exposure and washing are incorporated before color development.

[0034]

The examples described below are intended to illustrate the invention and are not intended to limit the invention.

[0035]Example 1 If the following replenisher is used at the indicated flow rate
Bleach-fix tank, similar to the tank that would be formed
(Bleach-fix 2) was prepared. Replenisher component A: sodium thiosulfate (2.75 mol),
Potassium sulfite (0.48 mol), 12.9 ml / m²so
Solution replenishment Replenisher solution component B: EDTA ferric ammonium (1.56
Mol), 4.3 ml / m ²Replenisher with replenisher Replenisher component C: acetic acid (8.5 mol), 4.3 ml / m²so
Refill 43 ml carryover in all of these calculations
/ M²Suppose

A simulated seasoning ammonium thiosulfate-containing bleach-fixer (bleach-fixer 1) was also prepared.

Table I Bleach-fix tank 1 Ammonium thiosulfate 0.55 mol Potassium sulfite 0.1 mol EDTA Ferric ammonium 0.1 mol pH (adjusted with K ₂ CO ₃ ) 6.1 Bleach-fix tank 2 thio Sodium Sulfate 0.55 mol Potassium Sulfite 0.1 mol EDTA Ferric Ammonium 0.1 mol pH (adjusted with K ₂ CO ₃ ) 6.1

Kodak Color Edge® photographic paper was processed using Kodak Process RA-4 with the following processing times and steps: Development 45 seconds 95 ° F Bleach-fix (bleach-fix 1 45 seconds 95 ° F or bleach-fix 2) Wash 90 seconds 95 ° F

The silver remaining in the photographic paper is replaced by D of the photographic paper.
It was determined by measuring the IR concentration of both max and Dmin and calculating the difference. The difference thus obtained was used as a measure of retained silver. For a fully bleached sample, the difference is expected to be 0.06 or less. The retained silver remaining in the photographic paper is shown in Table II.

Table II Silver (IR Dmax-Dmin) Bleaching-Fixing Bath Silver (Dmax-Dmin) 1 (Comparative) 0.06 2 (Invention) 0.06 Residual in Printing Paper After Processing

The above results show that the removal of silver from the photographic paper is satisfactory in both cases by the bleach-fix solution using sodium thiosulfate as fixing agent and by the solution using ammonium thiosulfate as fixing agent. It shows that it was possible to do. Following this experiment,
The following bleach-fix solution was prepared.

Table III Component 1 Bleach-Fixing Replenisher 3 Sodium thiosulfate 0.99 mol Potassium sulfite 0.18 mol Ferric ammonium EDTA 0.18 mol pH (adjusted with K ₂ CO ₃ ) 4.8 Bleach- Fixing tank 4 Sodium thiosulfate 0.55 mol Potassium sulfite 0.1 mol EDTA Ferric ammonium 0.1 mol pH (adjusted with K ₂ CO ₃ ) 6.1

Bleach-Fix Replenisher 3 has a replenishment rate of 53.8.
ml / m ² and assuming the carry-over 43 ml / m ² Bleach - fixing tank 4 - and the replenisher monocomponent required to obtain the (used in Table I bleach same to the fixing tank 2). Both solutions 3 and 4 were stored at room temperature for 8 weeks. Precipitation (ferric sodium EDTA) was observed in bleach-fix replenisher 3 but bleach-fix tank 4
It was absent. These results indicate that a one-component bleach-fix replenisher, such as Bleach-Fix Replenisher 3, cannot be used to replenish the bleach-fix tank 4 due to the instability of the solution. Have proved. The present invention avoids this problem.

[0044]Example 2 The following replenishers can also be used at the indicated flow rates.
Came. Replenisher component A: potassium thiosulfate (2.75 mol), sub
Potassium sulfate (0.48 mol), 12.9 ml / m²Melted in
Liquid replenishment Replenishing liquid component B: EDTA ferric ammonium (1.56
Mol), 4.3 ml / m ²Replenisher with replenisher Replenisher component C: acetic acid (8.5 mol), 4.3 ml / m²so
Refill 43 ml carryover in all of these calculations
/ M²Suppose

Example 3 The following replenisher solutions could also be used at the stated flow rates. Replenisher component A: sodium thiosulfate (2.4 mol) or potassium thiosulfate (2.4 mol), potassium sulfite (0.44 mol), solution replenishment at 16.1 ml / m ² Replenisher component B: EDTA No. Potassium diiron (1.3 mol), supplemented with 5.4 ml / m ² Replenisher component C: acetic acid (7.3 mol), supplemented with 5.4 ml / m ^{2 In} all of these calculations, carryover 43 ml
/ M ² is assumed.

Example 4 The following replenisher solutions could also be used at the flow rates indicated. Replenisher solution component A: sodium thiosulfate (2.7 mol) or potassium thiosulfate (2.7 mol), potassium sulfite (0.44 mol), solution replenishment at 32.3 ml / m ² Replenisher solution component B: EDTA No. Sodium diiron (0.245
Mole), 64.6ml / m ² supplemented Replenisher Part C: acetic acid (7.5 mol), 10.8ml / m ²
Refill with in all of these calculations, carryover 43 ml
/ M ² is assumed.

Example 5 A simulated bleach-fix tank was prepared as follows.

Table IV Bleach-fix tank 5 Ammonium thiosulfate 0.57 mol Sodium sulfite 0.14 mol Ferric ammonium EDTA 0.15 mol Mercaptotriazole 0.003 mol pH (adjusted with K ₂ CO ₃ ) 6.5 Bleach-fixing tank 6 Sodium thiosulfate 0.57 mol Sodium sulfite 0.14 mol Ferric ammonium EDTA 0.15 mol Mercaptotriazole 0.003 mol pH (adjusted with K ₂ CO ₃ ) 6.1

Ektachrome glossy photographic paper was processed using Kodak Process R-3 with the following processing times and steps. First development 75 seconds 38 ° C First wash 90 seconds 35-41 ° C Re-exposure by fluorescence 5-10 seconds Color development 135 seconds 38 ° C Second wash 45 seconds 25-41 ° C Bleach-fix (bleach-fix 5 120 seconds 38 ℃ or bleach-fixing 6) Final wash 135 seconds 25-41 ℃ Dry when needed Below 71 ℃

The silver remaining in the photographic paper is changed to D of the photographic paper.
It was determined by measuring the IR concentration of both max and Dmin and calculating the difference. The difference thus obtained is used as a measure of retained silver. For a fully bleached sample, the difference is expected to be 0.06 or less. The retained silver remaining in the photographic paper is shown in Table V.

Table V Silver (IR Dmax-Dmin) Bleaching-Fixing Bath Silver (Dmax-Dmin) 5 (Comparative) 0.06 2 (Invention) 0.06

The above results show that the removal of silver from the photographic paper was satisfactorily in both cases by the bleach-fix solution using sodium thiosulfate as fixing agent and by the solution using ammonium thiosulfate as fixing agent. It shows that it was possible to do. Following this experiment,
The following bleach-fix solution was prepared.

Table VI Component 1 Bleach-fixing replenisher 7 Sodium thiosulfate 0.65 mol Sodium sulfite 0.16 mol Ferric ammonium EDTA 0.18 mol Mercaptotriazole 0.004 mol pH (adjusted with K ₂ CO ₃ ) 6.0 Bleach-fixing tank 8 Sodium thiosulfate 0.57 mol Sodium sulfite 0.14 mol Ferric ammonium EDTA 0.15 mol Mercaptotriazole 0.003 mol pH (adjusted with K ₂ CO ₃ ).

Bleach-fix replenisher 7 has a replenishment rate of 215 ml.
/ M ² and carryover of 32.3 ml / m ² means one component replenisher necessary to obtain bleach-fix tank 8 (same as bleach-fix tank 6 used in Table IV). . Both bleach-fix replenisher 7 and bleach-fix tank 8 solutions were stored at room temperature for 8 weeks. Precipitation (sodium ferric EDTA) was observed in bleach-fix replenisher 7 but absent in bleach-fix tank 8. These results indicate that a one-component bleach-fix replenisher, such as bleach-fix replenisher 7, cannot be used to replenish bleach-fix tank 8 due to the instability of the solution. Have proved. The present invention avoids this problem.

Although the present invention has been described in detail with particular reference to preferred embodiments thereof, it is understood that various modifications and changes can be made within the spirit and scope of the invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Thomas P. Clives, The Third United States, New York 14616, Rochester, Judian Drive 330

Claims (2)

[Claims] 1. A replenisher for a bleach-fix solution, comprising:
Comprising separate and independent components A, B and C, wherein component A contains thiosulfate and a preservative, component B contains aminopolycarboxylic acid ferric complex and component C contains A bleach-fix replenisher containing an acid and having a total ammonium ion content of components A and B of less than 50 mol% of the total cations. 2. A method of replenishing a bleach-fix solution, comprising:
The bleach-fix solution contains separate and independent components A, B and C, wherein component A contains thiosulfate and a preservative and component B contains an aminopolycarboxylic acid ferric complex. Component C contains an acid, and the total ammonium ion content of Components A and B is less than 50 mol% of the total cation replenisher, and the pH of the bleach-fixer is 5.5-6.5. A method of replenishing a bleach-fixing solution, characterized in that each component of the replenishing solution is directly added to the bleach-fixing solution.