EP0552511A1 - Verfahren zur pH-Wertkontrolle eines Ascorbinsäureentwicklers - Google Patents

Verfahren zur pH-Wertkontrolle eines Ascorbinsäureentwicklers Download PDF

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Publication number
EP0552511A1
EP0552511A1 EP92204039A EP92204039A EP0552511A1 EP 0552511 A1 EP0552511 A1 EP 0552511A1 EP 92204039 A EP92204039 A EP 92204039A EP 92204039 A EP92204039 A EP 92204039A EP 0552511 A1 EP0552511 A1 EP 0552511A1
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EP
European Patent Office
Prior art keywords
developer
developing
solution
ascorbic acid
redox
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP92204039A
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English (en)
French (fr)
Inventor
Stefaan c/o Agfa-Gevaert N.V. Lingier
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Agfa Gevaert NV
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Agfa Gevaert NV
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Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Publication of EP0552511A1 publication Critical patent/EP0552511A1/de
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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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03D—APPARATUS FOR PROCESSING EXPOSED PHOTOGRAPHIC MATERIALS; ACCESSORIES THEREFOR
    • G03D3/00—Liquid processing apparatus involving immersion; Washing apparatus involving immersion
    • G03D3/02—Details of liquid circulation
    • G03D3/06—Liquid supply; Liquid circulation outside tanks
    • G03D3/065—Liquid supply; Liquid circulation outside tanks replenishment or recovery apparatus

Definitions

  • the present invention relates to a method of developing an exposed radiation-sensitive silver halide material by means of a photographic ascorbic acid developer wherein the activity level of the developer is maintained at a constant level by the controlled addition of alkali solution by means of an electrochemical sensing device.
  • Replenishment procedures are often adopted in photographic processing applications where there is a large throughput of film to be processed and the quantity of developer in the tank is usually at least several liters.
  • Typical examples are bulk processing of colour film either continuously or in batches, machine processing of X-ray film, and the processing for graphic arts applications of continuous tone or high contrast (litho) film, either manually in tanks or by automatic machine.
  • a replenisher solution is to readjust the concentration of the important components of the developer solution to a standard value.
  • the components which are considered are e.g. developing agents, halide ion, sulphite ion and buffering agents, the concentration of which has to be increased from time to time, and oxidation products, the concentration of which has to be decreased from time to time.
  • a method has been published which is able to keep the activity of a developer solution at a constant level by means of a controlled replenishing based on the oxidation state of the developer which is measured by means of a redox electrode system (GB 1,313,796).
  • This method can be very useful when aerial oxidation or oxidation through development leads to a decrease in activity of the developer as the result of a decrease in concentration of developing agent(s), and nearly no changes in pH occur due to the presence of buffers.
  • Replenishing then means adding a solution of developing agent in order to keep the concentration of the agent and hence the activity of the developer constant.
  • an ecologically safe developer e.g. a developer containing ascorbic acid or an analoguous compound as developing agent, preferably contains substantially no sulphite and no buffers for ecological reasons.
  • a kind of such a developer containing a rather high concentration of ascorbic acid or a related compound, and showing a rather high pH in order to obtain excellent lith quality, is disclosed in European Patent Application, filed 1991-02-14, appl . No. 91200311.8.
  • the activity depends on the concentration of the active developing species which are likely to be the mono- and dianion of ascorbic acid or analogue as described by Willis and Pontius in Phot. Sci. Eng. Vol .
  • the above objects are accomplished by a method of developing an exposed radiation-sensitive silver halide material by means of a developing solution containing an ascorbic acid type developing agent, characterized in that the alkalinity of the developing solution is maintained at a desired constant pH level by means of a redox potential measuring system, in casu a redox electrode pair.
  • the ascorbic acid type developing agent is represented by following general formula (I): wherein X represents an oxygen atom or an imino group, and n represents a positive integer from 1 to 4, and R represents a hydroxy group when n is 1, and R represents a hydroxy group or a hydrogen atom when n is 2 to 4.
  • Preferred compounds for use in accordance with the present invention are l-ascorbic acid and iso-ascorbic acid.
  • the apparatus for carrying out the method of the invention wherein the pH of an ascorbic acid type developer is maintained at the desired level comprises means for feeding an alkali solution to the developer and means for controlling the addition of an alkali solution, said control means being a redox electrode system.
  • a replenisher solution(s) can be added based on film throughput, on regular time basis or through manual intervention in order to keep the concentration of the developing agent constant. Both keeping the pH and concentration of ascorbic acid leads to a constant activity level of the ascorbic acid type developer.
  • the most preferred developing agents for use in accordance with the present invention are l-ascorbic acid and iso-ascorbic acid.
  • Other useful compounds include imino-l-ascorbic acid, 6-desoxy-l-ascorbic acid, l-rhamnoascorbic acid, l-fucoascorbic acid, d-glucoheptoascorbic acid, d-glucoascorbic acid, l-erythroascorbic acid, and their stereoisomers.
  • the developing agents can be incorporated in the developing solution in the free acid form or as a salt, preferably an alkali salt.
  • the developer solution is contained within a processing tank 1 (e.g. making part of a RAPILINE 66 processor, marketed by AGFA-GEVAERT N.V.) wich is equipped with a sensing device in the form of a redox electrode system 2.
  • the permanent pH measuring is effected by this redox electrode measuring system consisting of e.g. a carbon electrode / calomel reference electrode.
  • Other redox electrodes such as Pt, gold or glassy carbon can be used.
  • the replenisment with solution A in tank 3 having the same chemical composition of the developer solution is added to the processing tank by means of pump 4 based on film throughput.
  • the flow of replenisher A can be varied.
  • the alkali solution B in tank 5 contains an alkali solution, preferably an alkali hydroxide solution, e.g. a 50% KOH solution, and is added to the processing tank through pump 6 (e.g. Prominent Electronic E) which is controlled by the permanent measuring device 2.
  • the alkali solution may also contain agents which can adjust the development activity of a photographic silver halide developer solution such as stabilizers, activators and halide ions.
  • the measuring device produces a signal dependent on the state of oxidation of the developer solution and the value of said signal is compared with a reference signal generated by device 7 (e.g. a Metrohm Impulsomat 64).
  • the difference signal resulting from said comparison controls the flow of the alkali solution B until the difference signal is reduced substantially to zero.
  • the difference signal is converted into a timing pulse which is employed to actuate the appropiate relay unit which is incorporated in device 7 to control the operation of the associated replenisher pump.
  • the pulses created by the timing pulse generator 7 are employed to generate a ramp function serving as the reference signal with which the output voltage from the electrode system is compared in order to produce an output pulse whose duration varies in dependence on the magnitude of the difference between the reference potential and the output from the electrode system.
  • This output pulse is fed to the associated relay unit to control the operation of the pump 6, connected thereto.
  • Replenisher pump 6 may be replaced by a control valve operated by the relay unit and controlling the flow of the alkali solution B from its storage container 5.
  • a control valve operated by the relay unit operated by the relay unit and controlling the flow of the alkali solution B from its storage container 5.
  • Ascorbic acid type developing agent required for high lith quality
  • aerial oxidation will nearly not affect the ascorbic acid concentration. Therefore, when no film is processed the pH and hence activity of the developer solution is then permanently held constant only by means of the redox potential controlled addition of alkali solution B. From this description it is also clear that the activity level of the developer solution can be varied by altering the reference potential with which the redox potential of the solution is compared.
  • the developing solutions used in accordance with the present invention can be employed to develop various types of photographic black-and-white materials, e.g. amateur and professional materials for still photography, radiographic recording and duplicating materials, cinematographic recording and duplicating materials, and microfilm.
  • the merits of the present invention become most obvious in developing camera or duplicating materials for graphic arts in view of the importance of exact reproduction of line and screen dot originals. In this case the best results are obtained when applying these ascorbic acid type developing solutions to photographic materials containing negative chlorobromide emulsions as is commonly the case in various types of graphic arts materials.
  • chlorobromide emulsions in connection with an ascorbic acid developer are cubic, essentially (iodo)bromide, emulsions showing epitaxial deposition of a minor amount of chloride (about 1 to 5 %) on their corners. It was stated experimentally that an example of such an emulsion showed a selective speed advantage in ascorbic acid type developers compared to classical hydroquinone-Phenidone developers which was not found with a comparable (iodo)bromide emulsion showing no epitaxial chloride deposition. This kind of epitaxial deposition proved to be especially beneficial in the case of core-shell type emulsions.
  • Two emulsions showing the same grain size were prepared both comprising a AgBrI core with 4% of iodide and a AgBrCl shell with 5 % of chloride.
  • the chloride was distributed homogeneously over the shell while in the second case it was deposited epitaxially on the crystal corners. While the first emulsion lost about 0.10 log Et relative speed in an ascorbic acid developer compared to a hydroquinone-Phenidone developer this was not the case with the emulsion showing epitaxy which completely maintained its sensitivity.
  • a typical graphic arts chlorobromide emulsion was prepared by a double jet technique.
  • the silver halide composition was 83.6 mole % of chloride, 16 mole % of bromide and 0.4 mole % of iodide, and the average grain size was 0.27 micron.
  • the emulsion was chemically ripened to an optimal fog-sensitivity relationship and then spectrally sensitized to the blue and the green spectral region.
  • the emulsion was stabilized by means of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene.
  • a conventional coating aid and a conventional hardener the emulsion was coated on one side of a transparent polyethylene terephtalate support at a silver coverage of 6.25 g/m2, expressed as AgNO3/m2.
  • Dried coated samples of the prepared photographic material were exposed by a conventional white light source, on the one hand through a continuous tone wedge, on the other hand through a contact screen with a ruling of 54 lines/cm combined with a continuous tone wedge.
  • the developer composition was : iso-ascorbic acid 150 g/l 1-phenyl-5-mercaptotetrazole 80 mg/l potassium bromide 30 g/l 50 % KOH solution to adjust pH to 12.5

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Control Of Non-Electrical Variables (AREA)
EP92204039A 1992-01-20 1992-12-21 Verfahren zur pH-Wertkontrolle eines Ascorbinsäureentwicklers Withdrawn EP0552511A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP92200148 1992-01-20
EP92200148 1992-01-20

Publications (1)

Publication Number Publication Date
EP0552511A1 true EP0552511A1 (de) 1993-07-28

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EP92204039A Withdrawn EP0552511A1 (de) 1992-01-20 1992-12-21 Verfahren zur pH-Wertkontrolle eines Ascorbinsäureentwicklers

Country Status (2)

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EP (1) EP0552511A1 (de)
JP (1) JPH05313318A (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0708363A1 (de) * 1994-10-21 1996-04-24 Kodak Limited Verfahren und Vorrichtung zum Ändern des pH-Wertes einer photographischen Entwicklerlösung
EP0731381A1 (de) * 1995-02-21 1996-09-11 Agfa-Gevaert N.V. Entwicklerlösung und Verfahren zum Entwickeln eines belichteten, photographischen Silberhalogenidmaterials
EP0732619A1 (de) * 1995-02-21 1996-09-18 Agfa-Gevaert N.V. Entwicklerlösung und Verfahren zum Entwickeln eines belichteten photographischen Silberhalogenidmaterials
US5702875A (en) * 1996-06-28 1997-12-30 Eastman Kodak Company Weakly alkaline ascorbic acid developing composition, processing kit and method using same
FR2798467A1 (fr) * 1999-09-13 2001-03-16 Eastman Kodak Co Dispositif de mesure automatique de la concentration d'un agent developpateur
US6379877B1 (en) 1995-02-21 2002-04-30 Agfa-Gevaert Method for developing an exposed photographic silver halide material
CN108645970A (zh) * 2018-05-10 2018-10-12 深圳市志凌伟业技术股份有限公司 一种一体化的显影段药水槽pH值测试装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE767741C (de) * 1941-06-13 1953-07-20 Johannes Dr-Ing Hab Rzymkowski Verfahren zum Entwickeln von photographischen Metallsalzschichten
FR2089924A5 (de) * 1970-04-20 1972-01-07 Ipc Services Ltd
US3964912A (en) * 1974-09-09 1976-06-22 Eastman Kodak Company Ruthenium containing photographic developers
DE2738981A1 (de) * 1976-09-02 1978-03-09 Ibm Konzentrationssteuerung in prozessfluessigkeiten
US4505565A (en) * 1981-12-22 1985-03-19 Hiroshi Tanaka Device for detecting aging of developer for automatic film developing apparatus
EP0498968A1 (de) * 1991-02-14 1992-08-19 Agfa-Gevaert N.V. Photographisches Entwicklungsverfahren, in dem ein Ascorbin-Säure-Derivat eingesetzt wird

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE767741C (de) * 1941-06-13 1953-07-20 Johannes Dr-Ing Hab Rzymkowski Verfahren zum Entwickeln von photographischen Metallsalzschichten
FR2089924A5 (de) * 1970-04-20 1972-01-07 Ipc Services Ltd
US3964912A (en) * 1974-09-09 1976-06-22 Eastman Kodak Company Ruthenium containing photographic developers
DE2738981A1 (de) * 1976-09-02 1978-03-09 Ibm Konzentrationssteuerung in prozessfluessigkeiten
US4505565A (en) * 1981-12-22 1985-03-19 Hiroshi Tanaka Device for detecting aging of developer for automatic film developing apparatus
EP0498968A1 (de) * 1991-02-14 1992-08-19 Agfa-Gevaert N.V. Photographisches Entwicklungsverfahren, in dem ein Ascorbin-Säure-Derivat eingesetzt wird

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPIL Week 8449, Derwent Publications Ltd., London, GB; AN 84-304553 & JP-A-59 191 035 (FUJI PHOTO FILM KK) 30 October 1984 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0708363A1 (de) * 1994-10-21 1996-04-24 Kodak Limited Verfahren und Vorrichtung zum Ändern des pH-Wertes einer photographischen Entwicklerlösung
US5670303A (en) * 1994-10-21 1997-09-23 Eastman Kodak Company Method and apparatus for altering the pH of a photographic developing solution
EP0731381A1 (de) * 1995-02-21 1996-09-11 Agfa-Gevaert N.V. Entwicklerlösung und Verfahren zum Entwickeln eines belichteten, photographischen Silberhalogenidmaterials
EP0732619A1 (de) * 1995-02-21 1996-09-18 Agfa-Gevaert N.V. Entwicklerlösung und Verfahren zum Entwickeln eines belichteten photographischen Silberhalogenidmaterials
US6379877B1 (en) 1995-02-21 2002-04-30 Agfa-Gevaert Method for developing an exposed photographic silver halide material
US5702875A (en) * 1996-06-28 1997-12-30 Eastman Kodak Company Weakly alkaline ascorbic acid developing composition, processing kit and method using same
US5756271A (en) * 1996-06-28 1998-05-26 Eastman Kodak Company Weakly alkaline ascorbic acid developing composition, processing kit and method using same
FR2798467A1 (fr) * 1999-09-13 2001-03-16 Eastman Kodak Co Dispositif de mesure automatique de la concentration d'un agent developpateur
EP1085321A1 (de) * 1999-09-13 2001-03-21 Eastman Kodak Company Vorrichtung für die automatische Konzentrationsmessung einer Entwicklersubstanz
CN108645970A (zh) * 2018-05-10 2018-10-12 深圳市志凌伟业技术股份有限公司 一种一体化的显影段药水槽pH值测试装置
CN108645970B (zh) * 2018-05-10 2020-11-03 深圳市志凌伟业技术股份有限公司 一种一体化的显影段药水槽pH值测试装置

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Publication number Publication date
JPH05313318A (ja) 1993-11-26

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