EP0071344A1 - Stabiler photographischer Entwickler und Regenerator dafür - Google Patents

Stabiler photographischer Entwickler und Regenerator dafür Download PDF

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Publication number
EP0071344A1
EP0071344A1 EP82303437A EP82303437A EP0071344A1 EP 0071344 A1 EP0071344 A1 EP 0071344A1 EP 82303437 A EP82303437 A EP 82303437A EP 82303437 A EP82303437 A EP 82303437A EP 0071344 A1 EP0071344 A1 EP 0071344A1
Authority
EP
European Patent Office
Prior art keywords
developer
replenisher
photographic
processing
film
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.)
Granted
Application number
EP82303437A
Other languages
English (en)
French (fr)
Other versions
EP0071344B1 (de
Inventor
Peter Wuelfing, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0071344A1 publication Critical patent/EP0071344A1/de
Application granted granted Critical
Publication of EP0071344B1 publication Critical patent/EP0071344B1/de
Expired legal-status Critical Current

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Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29Development processes or agents therefor
    • G03C5/30Developers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29Development processes or agents therefor
    • G03C5/31Regeneration; Replenishers

Definitions

  • This invention is in the field of photographic silver halide developer solutions and replenishers therefor, and is specifically directed to developer-replenisher solutions useful in low through-put machine processing (developing) of photographic film.
  • processing solutions become exhausted by the passage of the exposed silver halide film and replenishment must be made to account for ingredient loss.
  • the processing fluids, especially the developer solution are degraded aerobically by contact with air and anerobically when simply left for long periods of inaction.
  • the other ingredients are set at concentrations which allow for the expected losses, the hydroquinone being offset by the antifoggants, without substantially affecting the sensitometry. In this situation a replenishment rate can be conveniently calculated based on the approximate area of film fed into the processor.
  • the present invention provides a replenisher formulation which is aimed at compensating for developer changes caused by nonuse,and not by the development reaction.
  • the replenisher is characterized by a pH lower than that of the developer, and it contains the maximum amount of bromide consistent with acceptable sensitometry.
  • pH will remain constant or slightly decrease, the bromide will remain essentially constant, and the other changes will compensate as in state of the art formulations.
  • the developer composition can maintain a useful lifetime equivalent to the high throughput processors.
  • a further object is to provide a developer/replenisher system particularly useful for machine processing of X-ray film when low throughput of film is practised.
  • an aqueous processing solution useful as a photographic developer bath for automatic processing of silver halide photographic film, particularly X-ray film, and as a replenisher therefor, consisting essentially of, per liter: with the proviso that the replenisher solution will not only contain bromide ion but also will have a lower pH than that of the developer solution.
  • a further embodiment of the invention is a process for the automatic processing of exposed photographic silver halide X-ray film wherein the imagewise exposed X-ray film is developed in a photographic developer bath comprising a photographic developer, bromide ion, an alkaline material and buffer system to maintain the pH of the developer bath at a desired value, an organic antifoggant and film speed restrainer, and water; the developed X-ray film is fixed, washed and dried; and the developer bath is replenished by a replenisher solution to maintain constant the photographic properties of the developer bath during processing of a large quantity of exposed X-ray film, characterized in that the processing solution described above serves as both the developer bath and the replenisher solution; with the proviso that the latter have a pH lower than that of the developer.
  • the processing solution of this invention can be used for both the developer and the replenisher therefor.
  • the replenisher solution has a lower pH than that of the developer
  • a small amount of base alkaline material
  • the replenisher is added to the developer bath as needed, based on time and/or the amount of film processed, thus compensating for both forms of developer exhaustion. It is surprising that this particular formulation can be used so successfully for low throughput in automatic processors since the differences between it and the prior art are so slight.
  • the difference in performance between the formulation of this invention and the prior art is very large.
  • a combination of 1-phenyl-3-pyrazolidone (sold under the Ilford trademark Phenidone) or a derivative thereof such as 4-methyl or 4,4-dimethyl phenidone, and hydroquinone or a derivative thereof such as chlorohydroquinone or bromohydroquinone is used.
  • This combination is particularly suited for automatic processing of X-ray films.
  • These ordinarily comprise a gelatino-AgBr, AgBrI, or AgClBrI emulsion on a film support such as polyethylene terephthalate.
  • the buffer system may be any convenient system, e.g., the borate and carbonate buffers conventionally used in X-ray developer baths are both suitable.
  • the organic antifoggant may be any organic antifoggant and film speed restrainer.
  • organic antifoggants are commonly employed in X-ray developer baths and include compounds of the benzimidazole, benzotriazole, benzothiazole, indazole, tetrazole, and thiazole group, as well as anthraquinone sulfonic acid salts.
  • Two or more organic antifoggants may be used. It is preferred to use a mixture of two antifoggants such as 5-nitroindazole and benzotriazole.
  • a range of bromide ion can be used successfully in this invention and provides excellent stability. 1 to 10 g/liter of KBr, for example, will provide sufficient bromide ion. NaBr may also be employed. Optimum amounts depend on replenishment rate and specific formula.
  • processing solution may include gelatin hardening agents, aerial oxidation r-estrainers, sequestering agents, surfactants, dyes, etc., as well known in the art. See, e.g., U.S. Patent 3,545,971 and "Photographic Processing Chemistry", supra, page 149 et seq.
  • Replenishment will be carried out at a rate per unit area of exposed film to provide processing of a large quantity of exposed film without change in sensitometric properties of the film, and will be determined empirically, as is known.
  • a suitable replenishment rate will be about 55 ml per 240 square inches of exposed film for development to normal radiographic density, using the processing solution of the invention.
  • Some processors have a standby replenishment mode. This 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 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. This replenishment is not effective with current developer/replenisher formulations but very effective with this invention since more of the correct replenisher is used.
  • the silver halide film is fixed, preferably in an acid fixer, and washed and dried in the usual manner. If a processing machine is used, these steps will be determined by the machine.
  • Example 1 is the best mode contemplated by the inventor of carrying out the invention.
  • Processing time was about 2-1/2 minutes at 92°F.
  • the processor was equipped with a conventional ammonium thiosulfate fixer solution.
  • D eveloper/replenisher I of Example 1 was operated for more than thirteen weeks at low throughput at St. Joseph's Hospital in Phoenix, Arizona in a Cronex QC-1 processor under essentially the same conditions as Example 1. The same formula was also run over four weeks at high throughput, thus demonstrating that developer/replenishers of this invention exhibit excellent stability over long periods of time in both high and low throughput.
  • a developer solution was made up as follows: Five gallons (approx. 19 liters) of this developer were charged to the processor described in Example 1. About 60 grams of acetic acid were added to the remaining 19 liters to give a pH of 10.0 + 0.05 and this was used as the replenisher. The processor was also charged with standard ammonium thiosulfate fixer and set at 92°F. Two samples of exposed X-ray film (high speed CRONEX®4, E. I. du Pont de Nemours and Company), 14 x 17 inch size, were processed (developed) and the sensitometry of the system checked with control strips as described in Example 1. The processor was then allowed to stand by for the remainder of the day.
  • Example 2 The formula of Example 2 (pH about 10.2) was used in this example, as both developer and replenisher, in the processor of Example 1. Under low throughput conditions (7 to 10 sheets of X-ray film/day) it served for more than five weeks. At the end of this period of time, control strips processed in this machine showed that the activity of the developer was well within limits and produced excellent results. A conventional developer of the prior art deteriorates badly in less than two weeks under these conditions and requires shut-down and cleaning of the automatic processor followed by re-charging with fresh solution.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP82303437A 1981-07-23 1982-06-30 Stabiler photographischer Entwickler und Regenerator dafür Expired EP0071344B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US28633181A 1981-07-23 1981-07-23
US286331 1981-07-23

Publications (2)

Publication Number Publication Date
EP0071344A1 true EP0071344A1 (de) 1983-02-09
EP0071344B1 EP0071344B1 (de) 1986-01-29

Family

ID=23098119

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82303437A Expired EP0071344B1 (de) 1981-07-23 1982-06-30 Stabiler photographischer Entwickler und Regenerator dafür

Country Status (8)

Country Link
EP (1) EP0071344B1 (de)
JP (1) JPS5837644A (de)
AU (1) AU554484B2 (de)
CA (1) CA1181624A (de)
DE (1) DE3268792D1 (de)
MX (1) MX161751A (de)
NZ (1) NZ201355A (de)
ZA (1) ZA825244B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0126644A2 (de) * 1983-05-20 1984-11-28 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial für Röntgenphotographie
EP0295078A2 (de) * 1987-06-09 1988-12-14 Minnesota Mining And Manufacturing Company Automatisch behandelbares photographisches Element

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3431860A1 (de) * 1984-08-30 1986-03-06 Agfa-Gevaert Ag, 5090 Leverkusen Verfahren zur herstellung farbfotografischer bilder
JPH0679142B2 (ja) * 1985-10-18 1994-10-05 富士写真フイルム株式会社 現像処理方法
DE3789634T2 (de) * 1986-06-27 1994-08-04 Fuji Photo Film Co Ltd Verfahren zum Zuführen von Regenerationsflüssigkeit in einem automatischen Entwicklungsgerät.
JPH0648371B2 (ja) * 1986-11-07 1994-06-22 富士写真フイルム株式会社 Xレイ用ハロゲン化銀写真感光材料の処理方法
JPH0627932B2 (ja) * 1987-01-19 1994-04-13 富士写真フイルム株式会社 ハロゲン化銀写真感光材料の処理方法
JP2699003B2 (ja) * 1988-10-28 1998-01-19 コニカ株式会社 ハロゲン化銀写真感光材料の処理方法
DE3938573A1 (de) * 1989-11-21 1991-05-23 Du Pont Deutschland Verfahren zum entwickeln photographischer silberhalogenidaufzeichnungsmaterialien
WO2009116846A1 (es) 2008-03-19 2009-09-24 Adma Elena Faraon Chaul Huerta Obturador cilindrico escalonado tipo aguja para el control automatico del gasto de agua en tuberias

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3545971A (en) * 1966-06-28 1970-12-08 Eastman Kodak Co Rapid processing of photographic x-ray film
US3854948A (en) * 1971-05-15 1974-12-17 Minnesota Mining & Mfg New development composition for radiographic film
GB1429919A (en) * 1973-11-20 1976-03-31 Fuji Photo Film Co Ltd Method of developing silver halide photographic material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5648864B2 (de) * 1973-09-03 1981-11-18
US4046571A (en) * 1975-06-27 1977-09-06 Gaf Corporation Processing solution for use as photographic developer bath and replenisher therefor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3545971A (en) * 1966-06-28 1970-12-08 Eastman Kodak Co Rapid processing of photographic x-ray film
US3854948A (en) * 1971-05-15 1974-12-17 Minnesota Mining & Mfg New development composition for radiographic film
GB1429919A (en) * 1973-11-20 1976-03-31 Fuji Photo Film Co Ltd Method of developing silver halide photographic material

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0126644A2 (de) * 1983-05-20 1984-11-28 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial für Röntgenphotographie
EP0126644A3 (en) * 1983-05-20 1985-11-27 Konishiroku Photo Industry Co. Ltd. Light-sensitive silver halide photographic material for x-ray photography
EP0295078A2 (de) * 1987-06-09 1988-12-14 Minnesota Mining And Manufacturing Company Automatisch behandelbares photographisches Element
US4794070A (en) * 1987-06-09 1988-12-27 Minnesota Mining And Manufacturing Company Automatically processible photographic element comprising a non-silver halide layer containing bromide
EP0295078A3 (en) * 1987-06-09 1989-11-08 Minnesota Mining And Manufacturing Company Automatically processible photographic element

Also Published As

Publication number Publication date
JPS5837644A (ja) 1983-03-04
AU8629682A (en) 1983-01-27
AU554484B2 (en) 1986-08-21
EP0071344B1 (de) 1986-01-29
JPH0336204B2 (de) 1991-05-30
CA1181624A (en) 1985-01-29
NZ201355A (en) 1985-03-20
ZA825244B (en) 1984-03-28
DE3268792D1 (en) 1986-03-13
MX161751A (es) 1990-12-20

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