US3868253A - Process for the rapid processing of silver dye bleach material - Google Patents

Process for the rapid processing of silver dye bleach material Download PDF

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Publication number
US3868253A
US3868253A US333249A US33324973A US3868253A US 3868253 A US3868253 A US 3868253A US 333249 A US333249 A US 333249A US 33324973 A US33324973 A US 33324973A US 3868253 A US3868253 A US 3868253A
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US
United States
Prior art keywords
bath
silver
process according
bleach
baths
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.)
Expired - Lifetime
Application number
US333249A
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English (en)
Inventor
Max Marthaler
Ulrich Frauchiger
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.)
Ilford Imaging Switzerland GmbH
Original Assignee
Ciba Geigy AG
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 Ciba Geigy AG filed Critical Ciba Geigy AG
Application granted granted Critical
Publication of US3868253A publication Critical patent/US3868253A/en
Assigned to ILFORD AG, A CO. OF SWITZERLAND reassignment ILFORD AG, A CO. OF SWITZERLAND ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: CIBA-GEIGY AG
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/28Silver dye bleach processes; Materials therefor; Preparing or processing such materials
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/164Rapid access processing

Definitions

  • the present invention relates to a rapid processing method of silver bleach materials.
  • the bath sequence is: (1) silver developing bath, (2) dye bleach bath (3) bleach fixing bath, (4) silver halide fixing bath and (5) soaking bath. Baths (1) and (2) each contain dye bleach catalyst, the material passing from (1) directly into (2).
  • the whole processing is carried out at temperatures of 20 to 50C. The whole process lasts at most 6 minutes, the dwell time in the individual baths being at most 2 minutes.
  • the material is soaked after the dye bleach bath, the metallic silver is oxidised in a silver bleach bath, the material is again soaked and the silver salts are either converted into complexes which are insensitive to light (stabilisation process) or are eluted after conversion into watersoluble complexes (fixing process).
  • the process according to the invention for the rapid processing of silver dye bleach material using the bath sequence (1) silver developing bath, (2) dye bleach bath, (3) bleach-fixing bath, (4) silver halide fixing bath and (5) soaking bath, with both the silver develop ing bath (1) and the dye bleach bath (2) containing a dye bleach catalyst and the silver dye bleach material to be processed passing from a silver developing bath (1) directly into a dye bleach bath (2), is characterised in that the entire processing, from entry into the first bath l to leaving the last bath (5) lasts at most 6 minutes at tempeatures between 20 and 50C and that the dwell time in each individual bath is at most 2 minutes.
  • the acid dye bleach bath (2) follows, without intermediate soaking, onto an alkaline silver developing bath l which is appropriately free of carbonates, the concentration of the dye bleach catalyst in the silver developing bath (1) being so chosen, advantageously, that the loss in effectiveness of the dye bleach bath (2), caused by consumption and/or carrying over of the bath liquid, is reduced to a minimum.
  • the catalyst concentration in the silver developing bath is as a rule 10 percent to 300 percent higher than the concentration in the dye bleach bath.
  • the bleach-fixing bath according to the invention which preferably has a pH value of at most 4 and contains an oxidising agent which is effective in the acid bath, preferably a nitro compound, especially a nitrobenzenesulphonic acid such as, for example, 2,4-dinitrobenzenesulphonic acid, bleaches the silver very rapidly but is not capable of completing the fixing within the short time that it acts, so that, according to the invention, the material is additionally treated with a silver halide fixing bath which appropriately contains, in addition to a relatively rapidly acting silver salt solvent, a high amount of sulphite, for example more than 20 g/l, to act as a buffer against acid carried into the bath and to render carried-over oxidising agent harmless.
  • an oxidising agent which is effective in the acid bath
  • a nitro compound especially a nitrobenzenesulphonic acid such as, for example, 2,4-dinitrobenzenesulphonic acid
  • thiourea is used as the silver salt solvent in the bleach-fixing bath (3).
  • All baths including the soaking baths, can contain additives such as hardeners, wetting agents, optical brighteners and UV-protection agents.
  • the preferred processing temperature is between 30 and 40C.
  • the lightsensitive layers are present on at least one side of this carrier, preferably in the known arrangement, that is to say a red-sensitised silver halide emulsion layer. which contains a cyan'azo dyestuff, as the bottom layer, on top of this a green-sensitised silver halide emulsion layer which contains a magenta azo dyestuff, and uppermost a blue-sensitive halide emulsion layer which contains a yellow azo dyestuff.
  • the material can also contain base layers, intermediate layers, filter layers and protective layers but the total thickness of the laycrs should as a rule not exceed 20 [.L.
  • Phenazines, quinoxalines and pyrazines can preferably be employed as dye bleach catalysts for the process according to the invention.
  • the concentration of the baths can be so adjusted, by simple experiments, that the dwell times in the individual baths are in the ratio of small integers.
  • the ma terial can be processed in an automatic developing machine which contains 5 to 20 tanks and where the dwell time per tank is to 30 seconds.
  • the bath system according to the invention has proved particularly stable to contamination by bath material being carried over, so that constant results are obtained even after processing major amounts of exposed colour material.
  • Example 1 in the green-sensitive layer, above it, the magenta image dyestuff of the formula IIO S and in the topmost bluesensitive layer, the yellow image dyestuff of the formula s out
  • the image dyestuffs are incorporated into the emulsions at a reflectance density of D 2.0.
  • the colour layers, containing a total of 0.8 g of Ag/m are sepa- 7 rated by gelatine layers, the total thickness being ,u..
  • This material is exposed by flashlight in a commercially available automatic portrait machine and is sub- Na metaborate g/l 40 seconds 40 seconds 40 seconds tinoise Na bisulphite 10 g/l Passage time seconds 5 times, soaking bath Passage time seconds CH: S Oall 280 seconds Total processing time I 4 minutes 40 seconds)
  • After drying by means of warm air images having a good white, especially good white edge, and a true-tonature reproduction, in colour and tonal values, of the person photographed, are obtained. Even after the passage of 750 to 1,000 images of passport photograph size, 4 cm X 5 cm, over the course of l0 days, images of practically unchanged quality can still be produced.
  • Example 1 The process described in Example 1 is repeated. However, instead of the bleach-fixing bath according to the invention. a bath according to US Pat. Specification No. 3,335,004 (Example 1), of the. following composition, is employed:
  • Example 2 ln another type of automatic machine, only 10 tanks are available for processing; the dwell time is separately adjustable for each tank.
  • the exposed material here passes through the same baths as in Example 1, but with the following processing sequence (temperature C):
  • Process for the rapid processing of silver dye bleach materials which comprises using the bath sequence (l silver developing bath, (2) dye bleach bath, (3) bleach-fixing bath, (4) silver halide fixing bath and (5) soaking bath, with both the silver developing bath (1) and the dye bleach bath (2) containing a dye bleach catalyst and the silver dye bleach material to be processed passing from a silver developing bath 1) directly into a dye bleach bath (2), the entire processing, from entry into the first bath l to leaving the last bath (5) lasting at most 6 minutes at temperatures of 20 to 50C and the dwell time in the individual baths being at most 2 minutes.
  • bath sequence l silver developing bath, (2) dye bleach bath, (3) bleach-fixing bath, (4) silver halide fixing bath and (5) soaking bath, with both the silver developing bath (1) and the dye bleach bath (2) containing a dye bleach catalyst and the silver dye bleach material to be processed passing from a silver developing bath 1) directly into a dye bleach bath (2), the entire processing, from entry into the first bath l to leaving the last bath (5) lasting at most 6 minutes at temperatures of 20 to 50
  • Process according to claim 2 which comprises using a bleach-fixing bath (3) with a pH value of at most 4 and containing an oxidising agent which is effective in an acid bath and using a silver halide fixing bath (4) that contains, in addition to a relatively rapidly acting silver salt solvent, more than 20 g/l of sulphite.
  • Process according to claim 1 which comprises di viding at least one of the five baths into a plurality of units which are connected directly one behind the other.
  • Process according to claim 7 which comprises using several dye bleach baths (2).
  • Process according toclaim 7 which comprises using several bleach-fixing baths (3).
  • Process according to claim 7 which comprises using several silver halide fixing baths (4).
  • Process according to claim 7 which comprises using several soaking baths (5).

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US333249A 1972-02-28 1973-02-16 Process for the rapid processing of silver dye bleach material Expired - Lifetime US3868253A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH277072A CH576158A5 (de) 1972-02-28 1972-02-28

Publications (1)

Publication Number Publication Date
US3868253A true US3868253A (en) 1975-02-25

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
US333249A Expired - Lifetime US3868253A (en) 1972-02-28 1973-02-16 Process for the rapid processing of silver dye bleach material

Country Status (14)

Country Link
US (1) US3868253A (de)
JP (1) JPS48100136A (de)
AT (1) AT326479B (de)
BE (1) BE796005A (de)
CA (1) CA1006038A (de)
CH (1) CH576158A5 (de)
DE (1) DE2309526A1 (de)
ES (1) ES412087A1 (de)
FR (1) FR2174061B1 (de)
GB (1) GB1394657A (de)
IE (1) IE37290B1 (de)
IT (1) IT977510B (de)
NL (1) NL7302829A (de)
ZA (1) ZA731019B (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3961957A (en) * 1973-05-18 1976-06-08 Ciba-Geigy Ag Dye bleach preparation for the photographic silver dye bleach process
US3963492A (en) * 1973-10-12 1976-06-15 Ciba-Geigy Ag Method for processing silver dye bleach materials
US4014698A (en) * 1974-07-10 1977-03-29 Ciba-Geigy Ag Method for processing silver dye bleach materials
US4232112A (en) * 1978-02-10 1980-11-04 Konishiroku Photo Industry Co., Ltd. Process for treating silver halide color photographic photosensitive material
US4343892A (en) * 1979-05-11 1982-08-10 Fuji Photo Film Co., Ltd. Method and apparatus for silver recovery during photographic processing
US4868098A (en) * 1987-01-06 1989-09-19 Ciba-Geigy Ag Method of processing exposed photographic silver dye bleach materials comprising heating after processing liquid application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3156561A (en) * 1958-06-03 1964-11-10 Ciba Geigy Corp Method of producing color photographic pictures
US3394004A (en) * 1964-03-20 1968-07-23 Ciba Ltd Photographic material for the silver dyestuff bleaching process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3156561A (en) * 1958-06-03 1964-11-10 Ciba Geigy Corp Method of producing color photographic pictures
US3394004A (en) * 1964-03-20 1968-07-23 Ciba Ltd Photographic material for the silver dyestuff bleaching process

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3961957A (en) * 1973-05-18 1976-06-08 Ciba-Geigy Ag Dye bleach preparation for the photographic silver dye bleach process
US3963492A (en) * 1973-10-12 1976-06-15 Ciba-Geigy Ag Method for processing silver dye bleach materials
US4014698A (en) * 1974-07-10 1977-03-29 Ciba-Geigy Ag Method for processing silver dye bleach materials
US4232112A (en) * 1978-02-10 1980-11-04 Konishiroku Photo Industry Co., Ltd. Process for treating silver halide color photographic photosensitive material
US4343892A (en) * 1979-05-11 1982-08-10 Fuji Photo Film Co., Ltd. Method and apparatus for silver recovery during photographic processing
US4868098A (en) * 1987-01-06 1989-09-19 Ciba-Geigy Ag Method of processing exposed photographic silver dye bleach materials comprising heating after processing liquid application

Also Published As

Publication number Publication date
CH576158A5 (de) 1976-05-31
FR2174061A1 (de) 1973-10-12
NL7302829A (de) 1973-08-30
DE2309526A1 (de) 1973-09-06
IE37290L (en) 1973-08-28
IT977510B (it) 1974-09-20
CA1006038A (en) 1977-03-01
FR2174061B1 (de) 1976-05-21
JPS48100136A (de) 1973-12-18
BE796005A (fr) 1973-08-27
GB1394657A (en) 1975-05-21
ES412087A1 (es) 1975-12-01
IE37290B1 (en) 1977-06-22
ATA173973A (de) 1975-02-15
AT326479B (de) 1975-12-10
ZA731019B (en) 1973-11-28

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Legal Events

Date Code Title Description
AS Assignment

Owner name: ILFORD AG, A CO. OF SWITZERLAND, SWITZERLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CIBA-GEIGY AG;REEL/FRAME:005319/0226

Effective date: 19900502