EP0660175B1 - Steuerung der Nachfüllung und Regenerierung während der photographischen Entwicklung - Google Patents

Steuerung der Nachfüllung und Regenerierung während der photographischen Entwicklung Download PDF

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Publication number
EP0660175B1
EP0660175B1 EP19940119119 EP94119119A EP0660175B1 EP 0660175 B1 EP0660175 B1 EP 0660175B1 EP 19940119119 EP19940119119 EP 19940119119 EP 94119119 A EP94119119 A EP 94119119A EP 0660175 B1 EP0660175 B1 EP 0660175B1
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titratably
distinct
developer
component
method recited
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French (fr)
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EP0660175A2 (de
EP0660175A3 (de
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Peter Wuelfing
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Sterling Diagnostic Imaging Inc
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Sterling Diagnostic Imaging Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/31—Regeneration; Replenishers

Definitions

  • an image-wise exposed film must be processed to convert the latent image into a viewable negative of the image.
  • the processing operation requires a development step, wherein the exposed silver halide crystals are reduced to elemental silver, and a fix or bleach step wherein the unexposed silver halide crystals are removed from the film. It is also advantageous to wash the film prior to drying and viewing.
  • Ascorbic acid based developers are also used for reduction of exposed silver halide during development. Analogous depletion of active ingredients is observed with use.
  • Hydroquinone developers are also susceptible to air oxidation.
  • the chemical reaction associated with air oxidation is provided in Equation 2. Air oxidation of a hydroquinone developer does not effect the bromide level but the pH increases due to liberation of hydroxide ion as the sodium salt.
  • Evaporation of water is also known to occur. Loss of solvent can alter the concentration of ingredients and the reactivity. Yet another detrimental phenomenon is the physical removal of developer solution by the film.
  • Specific gravity is another analytical measurement which is often used during the initial makeup of the solutions. The inaccuracy and non-specificity of this method is well known in the art and diagnostic information is rarely obtained.
  • GB-A-1313796 discloses a method for measurement of halide by titration and of hydroquinone by redox titration employing multiple halide additions.
  • film which utilize tabular grains are known to exhibit sensitometric properties which vary with bromide level in the developer. Films with more conventional grains are known to be less sensitive to bromide level but sensitometric differences correlate more strongly to processing temperature and other changes in developer. This places a burden on the health care professional since different films could exhibit different properties in the same processor. To adequately use the indirect method a control film would have to be established for all types of films employed.
  • a particular deficiency of prior art tests is the lack of information on the activity of the replenisher chemicals.
  • the bromide titration, or indirect film methods only test the activity of the development solutions in the processor at the time of the test.
  • a single test provides no information about the replenishment conditions.
  • To obtain information on replenishment a subsequent test must be done and the data correlated to analyze for trends and/or the replenisher must be checked independently.
  • a film method is intrusive since the test film itself initiates the development reaction and some replenishment occurs to compensate therefor. Immediately after the control film is processed the conditions in the development solution will be different.
  • An improperly prepared replenisher may take a considerable amount of time (several hours to several days) to displace a sufficient amount of developer to be observed by a film test.
  • Nominal replenishment rates are sufficient to replace approximately half of the chemicals in the developer tank with replenisher chemicals in approximately 8-10 hours.
  • the full effect of incorrect replenishment, either rate or composition may not be noticed until the developer has been replaced by at least one equal volume of replenisher.
  • the lag time can span several days in some instances. Once an actual problem is detected the entire replenisher and developer must be replaced to correct the situation.
  • the tardiness of the test is especially critical if recommended procedures are followed in entirety. Corrective action is suggested only after three consecutive test are observed to generate a trend in any direction away from the norm. Typical test frequency is daily for most situations but the actual time can vary substantially. Therefore, many inferior films could be produced prior to running a control which may lead to an incorrect diagnosis or a need to repeat the exposure to the patient.
  • the practitioner is forced into one of the following two situations.
  • the first is a correct film measurement indicating the current chemistry may be correct but replenishment conditions are unknown. In this situation the practitioner typically continues operating with no knowledge of potential problems.
  • the second situation occurs when the film measurements are not correct. Based on the standard guidelines an initial check of obvious problems such as temperature, and the like, is suggested. If the problem is not resolved the processing and replenishment chemicals are usually discarded and replaced at a substantial financial and time burden to the medical professional.
  • developer/replenisher solution can be monitored independent of the film thereby decreasing the effects of film, exposure and density measurements on the development conditions.
  • Yet another object is a diagnostic test method which can determine if the replenisher or developer is properly mixed and which can provide diagnostic information for correcting an improperly prepared solution.
  • a particular feature of the present invention is the ability to determine quantitative information rapidly and with minimal cost.
  • Chemical developers are specifically formulated to efficiently reduce image-wise exposed silver halide to elemental silver.
  • the developer typically comprises a reducing agent, optional antifoggants, optional pH buffers, optional hardeners and optional stabilizers.
  • Each of at least two components of the replenisher further comprise compounds which are analytically distinct one from the other when the components are mixed.
  • analytically distinct refers to compounds which are titratably distinct.
  • Preferred titratably distinct components are anions which form silver salts and which do not adversely interfere with the photographic development or fix process. It is particularly important that the silver salts formed have sufficient solubility that premature precipitation does not alter the results.
  • Preferred is a salt with a solubility product (Ksp) of 10 -6 to 10 -20 .
  • Ksp solubility product
  • Specifically preferred are combinations of anions which form silver salts with sufficient differences in solubility product to be quantitatively separatable in a potentiometric titration.
  • the solubility products of the silver salts, measured as Ksp are preferably different by at least 10 -2 using current titration abilities under ambient conditions.
  • the bromide is one titrant and the other titrants are chosen accordingly. Chloride has been found to be particularly preferred as a second titrant due to the low cost, photographic inert properties, solubility and the like.
  • Preferred reducing agents are hydroquinone, 4-hydroxymethyl-1-phenyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, ascorbic acid, d-erythroascorbic acid (i.e. erythorbic or isoascorbic acid), d-glucosascorbic acid, 6-deoxy-l-ascorbic acid, d-glucoascorbic acid, d-galactoascorbic acid, l-glucoascorbic acid and l-alloascorbic acid.
  • d-erythroascorbic acid i.e. erythorbic or isoascorbic acid
  • d-glucosascorbic acid 6-deoxy-l-ascorbic acid
  • d-glucoascorbic acid d-galactoascorbic acid
  • l-glucoascorbic acid l-alloascorbic acid.
  • the unsubstituted compounds of this class of compounds may be represented by the formula: wherein X is an oxygen atom or imino group, R is any group which does not render the ascorbic acid water-insoluble and is a non-interfering group.
  • Non-interfering is defined as not causing steric hindrance, is not chemically reactive with other portions of the molecule, is not a coordination group for the molecule, and is not more electropositive than a saturated hydrocarbon residue.
  • R is preferably an aryl group, in particular an aryl group of 6-10 carbons, or a group of the formula R 1 (CH 2 )(CH 2 ) n-1 wherein n is a positive integer from 1 to 4 and R1 is either a hydrogen atom or hydroxyl group when n is 2 to 4 and is hydroxyl when n is 1.
  • R1 is either a hydrogen atom or hydroxyl group when n is 2 to 4 and is hydroxyl when n is 1.
  • ascorbic and erythorbic (iso-ascorbic) acid are preferred.
  • the developer may contain a multitude of conventional ingredients which serve functions well known in the art. Included are additional development agents, antifoggant agents, pH buffers, sequestering agents, swelling control agents and development accelerators. Materials which may be included in the processing solution, such as swelling control agents (i.e. gelatin hardening agents), aerial oxidation restrainers, sequestering agents, surfactants, dyes, well known in the art are exemplified in U.S. Pat. No. 3,545,971 and Photographic Processing Chemistry , L.F.A. Mason, 1966, page 149 et seq.
  • a developer pH of approximately 9-12 be maintained. More preferred is a developer pH of 9.7-10.6 and most preferred is a developer pH of 10.0 ⁇ 0.3.
  • Any alkaline material may be used to provide the required pH, such as sodium or potassium hydroxide, sodium or potassium carbonate.
  • the buffer system may be any convenient system, e.g., the borate and carbonate buffers conventionally used in X-ray developer baths are quite suitable.
  • the replenisher solution is ideally formulated such that addition to the developer restores the chemical composition of the developer to optimal composition under steady state conditions. It is typically preferred that the replenisher be substantially identical to the developer with the exception of the titratably distinct additives described herein.
  • the preferred developer composition and replenisher therefore comprises, per liter: 0.5 to 5.0 g of 1-phenyl-3-pyrazolidone or a derivative thereof; 15 to 35 g of hydroquinone, or a derivative thereof; 0 to 10 g of bromide ion; 0.01 to 6.0 mmoles of an organic antifoggant; 1.0 to 30.0 g of a titratably distinct ion and 0 to 30 g of a different titratably distinct ion.
  • the second titratably distinct ion is chloride.
  • Another preferred developer composition and replenisher comprises, per liter, 15.0 to 75.0 g of ascorbic acid; 0.5 to 5.0 g of 3-pyrazolidone or a suitable derivative thereof; 2 to 20 grams of sulfite; 15 to 30 grams of carbonate; 0 to 10 g of bromide ion; 0.01 to 6.0 mmoles of an organic antifoggant; 1.0 to 30.0 g of a titratably distinct ion and 0 to 30.0 g of a different titratably distinct ion.
  • a range of bromide ion can be used successfully in this invention. It is preferred that one of the titratably distinct ions be KBr in an amount equal to 1 to 10 g/liter. NaBr may also be employed. Optimum amounts depend on replenishment rate and specific formula.
  • a suitable replenishment rate will be 50-70 ml per 0.155 m 2 (240 square inches) of film (40% exposed) for development to normal radiographic density, using the processing solution of the invention as properly prepared.
  • Substantially all processors have some type of a standby replenishment mode. There are a lot of differences based on the manufacturer but the concept is usually similar.
  • the standby mode typically works as follows: if no film is passed in a given time, the processor goes into a standby mode which deactivates the drive train and dryer and reduces the water supply. After a given time, it comes back on for several minutes and then shuts off again. After a specified number of cycles, it replenishes a predetermined amount.
  • R1 - representing a properly prepared replenisher solution Water 700 ml Solution A 250 ml Solution B 25 ml Solution C 25 ml
  • R2 - representing a replenisher which is 10% overdiluted Solution
  • R1 250 ml Water 25 ml
  • R3 - representing a replenisher which is 15% overdiluted Solution
  • R4 - representing replenisher with proper dilution but 10% shortage of Solution
  • A Water 725 ml Solution A 225 ml Solution B 25 ml Solution C 25 ml
  • R5 - representing replenisher with proper dilution but 10% shortage of Solution C
  • R6 - representing a solution which is properly mixed but underdiluted by 10% Water 600 ml Solution A 250 ml Solution B 25 ml Solution C 25 ml
  • Standard pH and specific gravity measurements were taken and the halides were titrated using the following procedure.
  • a 10 ml sample was taken from each solution.
  • the sample was diluted to 120 ml with 0.1 N sulfuric acid.
  • the samples were then titrated for bromide ion and chloride ion, in triplicate, using the two endpoint potentiometric method on a Brinkman Model 702 automatic titrator using a silver billet electrode.
  • the halide ion concentration was reported as a sodium salt.
  • the pH was measured with a Fisher Accumet 915 pH meter equipped with a combination glass electrode as known in the art. Specific gravity was determined by weighing 10 ml samples. The results are listed in Table 1.
  • the replenisher illustrated is substantially identical to that described in U.S. Pat. No. 4,741,991.
  • This replenisher is intended to be used with a developer which has a steady state bromide level of 6.0 to 7.0 g/l as the sodium salt.
  • the development reaction would cause the bromide ion level to increase as film is developed in accordance with Equation 1.
  • the combined teachings of U.S. Pat. No. 4,741,991 and U.S. Pat. No. 3,970,457 would suggest that the replenisher is added in an amount sufficient to return the bromide ion level to the predetermined level.
  • a processor upset may be detected for each of R2 through R6 with no diagnostic information available based on the bromide ion titration alone.
  • a titration of the developer replenished with R1 would have the predetermined level of bromide ion and chloride ion.
  • a titration of the developer replenished with a set amount of R2 or R3 would have a bromide ion level which is lower than the predetermined level and a chloride ion level which is below the predetermined level.
  • a developer replenished with a set amount of R4 would have a bromide ion level which is lower than the predetermined level and a chloride ion level which is at the predetermined level.
  • a developer replenished with a set amount of R5 would have a bromide ion level which is at the predetermined level and a chloride ion level which is low.
  • a developer replenished with a set amount of R6 would have a bromide and chloride level which is above the predetermined levels. In all cases the incorrect solution could be immediately corrected by changing replenishment amount or adding one component of replenisher.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (12)

  1. Verfahren zur Umwandlung einer Serie von bildmäßig belichteten fotografischen Silberhalogenidfolien in beobachtbare Bilder, mit folgenden Stufen :
    (a) die Entwicklung einer bildmäßig belichteten Silberhalogenid-folie in einem ersten Entwickler mit einem pH zwischen 9 und 12, wobei dieser erste Entwickler die nachstehenden Ingredienzien enthält :
    eine Entwicklersubstanz in einer ersten Substanzkonzentration, eine erste titrierbar unterschiedliche Komponente in einer ersten Komponentenkonzentration und eine zweite titrierbar unterschiedliche Komponente in einer zweiten Komponentenkonzentration,
    wobei das belichtete Silberhalogenid zu elementarem Silber reduziert wird und sich der erste Entwickler abreichert, wodurch ein abgereicherter Entwickler erhalten wird, der die nachstehenden Ingredienzien enthält :
    die Entwicklersubstanz in einer zweiten Substanzkonzentration, die erste titrierbar unterschiedliche Komponente in einer ersten abgereicherten Komponentenkonzentration und die zweite titrierbar unterschiedliche Komponente in einer zweiten abgereicherten Komponentenkonzentration,
    (b) die Entfernung des unbelichteten Silberhalogenids von der fotografischen Folie mit Hilfe einer Fixierlösung,
    (c) die Titrierung des abgereicherten Entwicklers zur Ermittlung des Verhältnisses der ersten abgereicherten Komponentenkonzentration zur zweiten abgereicherten Komponentenkonzentration,
    (d) die Zugabe einer Nachfüllösung im abgereicherten Entwickler, wodurch ein nachgefüllter Entwickler erhalten wird, der die nachstehenden Ingredienzien enthält :
    die Entwicklersubstanz, die erste titrierbar unterschiedliche Komponente und die zweite titrierbar unterschiedliche Komponente,
    wobei der nachgefüllte Entwickler einen pH zwischen 9 und 12 aufweist und folgende Ingredienzien enthält :
    die Entwicklersubstanz in der ersten Substanzkonzentration, die erste titrierbar unterschiedliche Komponente in der ersten Komponentenkonzentration und die zweite titrierbar unterschiedliche Komponente in der zweiten Komponentenkonzentration,
    (e) die Wiederholung der Stufen (a) bis (d) für wenigstens eine zusätzliche bildmäßig belichtete Silberhalogenidfolie.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die erste titrierbar unterschiedliche Komponente und die zweite titrierbar unterschiedliche Komponente unabhängig voneinander Silbersalze mit einem Ksp-Wert zwischen 10-6 und 10-20 bilden.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Ksp-Wert der ersten titrierbar unterschiedlichen Komponente und der Ksp-Wert der zweiten titrierbar unterschiedlichen Komponente um wenigstens 10-2 auseinander liegen.
  4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die erste titrierbar unterschiedliche Komponente Bromid ist.
  5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die zweite titrierbar unterschiedliche Komponente Chlorid ist.
  6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Entwicklersubstanz 4-Hydroxymethyl-1-phenyl-3-pyrazolidon, 1-Phenyl-3-pyrazolidon, 4-Methyl-1-phenyl-3-pyrazolidon, 4,4-Methyl-1-phenyl-3-pyrazolidon, Hydrochinon, Chlorhydrochinon oder Bromhydrochinon ist.
  7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Nachfüllösung pro Liter zwischen 0,5 und 5,0 g 1-Phenyl-3-pyrazolin, zwischen 15 und 35 g Hydrochinon, zwischen 0 und 10 g Bromid, zwischen 0,01 und 6,0 Mmol eines organischen Schleierschutzmittels, zwischen 1,0 und 30,0 g des ersten titrierbar unterschiedlichen Tons und zwischen 0,0 und 30 g des zweiten titrierbar unterschiedlichen Tons enthält, wobei das zweite titrierbar unterschiedliche Ion nicht in einer Menge von 0,0 g pro Liter enthalten sein kann, wenn das Bromid in einer Menge von 0 g pro Liter enthalten ist.
  8. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Entwicklersubstanz wenigstens eine Verbindung aus der Gruppe bestehend aus Ascorbinsäure, Zucker-Derivaten von Ascorbinsäure, Stereoisomeren von Ascorbinsäure, Diastereoisomeren von Ascorbinsäure, Salzen von Ascorbinsäure und Gemischen derselben enthält.
  9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß die Entwicklersubstanz wenigstens eine Verbindung aus der Gruppe bestehend aus Ascorbinsäure, d-Erythroascorbinsäure (d.h. Erythorbinsäure oder Isoascorbinsäure), d-Glucosascorbinsäure, 6-Deoxy-l-ascorbinsäure, d-Glucoascorbinsäure, d-Galacto-ascorbinsäure, l-Guloascorbinsäure und l-Alloascorbinsäure enthält.
  10. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Nachfüllösung pro Liter zwischen 15,0 und 75,0 g Ascorbinsäure, zwischen 0,5 und 5,0 g 3-Pyrazolidon oder eines geeigneten Derivats davon, zwischen 2 und 20 g Sulfit, zwischen 15 und 30 g Carbonat, zwischen 0 und 10 g Bromid, zwischen 0,01 und 6,0 Mmol eines organischen Schleierschutzmittels, zwischen 1,0 und 30,0 g des ersten titrierbar unterschiedlichen Ions und zwischen 0 und 30 g des zweiten titrierbar unterschiedlichen Ions enthält, wobei das zweite titrierbar unterschiedliche Ion nicht in einer Menge von 0,0 g pro Liter enthalten sein kann, wenn das Bromid in einer Menge von 0 g pro Liter enthalten ist.
  11. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß die Entwicklersubstanz
    Figure 00240001
    enthält,
    wobei bedeuten :
    X ein Sauerstoffatom oder eine Iminogruppe,
    R eine Arylgruppe oder eine Gruppe der Formel R1(CH2)(CH2)n-1, wobei n eine positive ganze Zahl zwischen 1 und 4 und R1 entweder ein Wasserstoffatom oder eine Hydroxylgruppe bedeutet, falls n zwischen 2 und 4 liegt, und eine Hydroxylgruppe bedeutet, falls n 1 ist.
  12. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Entwicklersubstanz
    Figure 00240002
    ist,
    wobei X ein Sauerstoffatom oder eine Iminogruppe bedeutet und R irgendwelche Gruppe bedeuten kann, die die Ascorbinsäure nicht wasserunlöslich zu machen vermag und keine störende Gruppe ist.
EP19940119119 1993-12-22 1994-12-05 Steuerung der Nachfüllung und Regenerierung während der photographischen Entwicklung Expired - Lifetime EP0660175B1 (de)

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US168422 1993-12-22

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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1572094A1 (de) * 1966-12-03 1970-01-02 Klimsch & Co Verfahren zur Dosierung der Regeneratorloesung bei photographischen Entwicklungsmaschinen
GB1313796A (en) * 1970-04-20 1973-04-18 Ipc Services Ltd Photographic processing
US4741991A (en) * 1981-07-23 1988-05-03 E. I. Du Pont De Nemours And Company Stable photographic developer and replenisher therefor
EP0573700A1 (de) * 1992-06-09 1993-12-15 Agfa-Gevaert N.V. Regenierung eines Ascorbinsäure- und 3-Pyrazolidinonderivate enthaltenden Entwicklers

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DE69423587T2 (de) 2001-02-22
DE69423587D1 (de) 2000-04-27
EP0660175A3 (de) 1995-12-06
JPH07199418A (ja) 1995-08-04

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