EP0274357A2 - Procédé pour le traitement de matériaux photographiques exposés pour blanchiment des couleurs à l'argent - Google Patents

Procédé pour le traitement de matériaux photographiques exposés pour blanchiment des couleurs à l'argent Download PDF

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Publication number
EP0274357A2
EP0274357A2 EP87810786A EP87810786A EP0274357A2 EP 0274357 A2 EP0274357 A2 EP 0274357A2 EP 87810786 A EP87810786 A EP 87810786A EP 87810786 A EP87810786 A EP 87810786A EP 0274357 A2 EP0274357 A2 EP 0274357A2
Authority
EP
European Patent Office
Prior art keywords
processing liquid
process step
silver
color
bleaching
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.)
Pending
Application number
EP87810786A
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German (de)
English (en)
Other versions
EP0274357A3 (en
Inventor
Rolf Dr. Steiger
Urs Josef Dr. Fürholz
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
Ilford 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, Ilford AG filed Critical Ciba Geigy AG
Publication of EP0274357A2 publication Critical patent/EP0274357A2/fr
Publication of EP0274357A3 publication Critical patent/EP0274357A3/de
Pending legal-status Critical Current

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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/164—Rapid access processing

Definitions

  • the present invention relates to a method for processing exposed photographic silver color bleaching materials.
  • the object is achieved in that an amount of processing solution in the form of a thin liquid film which at most corresponds to the swelling volume is applied to the top layer of the exposed material and then the material is treated with heat.
  • the swelling volume of processing liquid is not only sufficient for development and fixation, but also for color and silver bleaching.
  • the method according to the invention also has the advantage that the material remains almost dry during processing.
  • the present invention thus relates to a process for processing exposed photographic silver color bleaching materials with the process steps (1) development, (2) color bleaching, (3) silver bleaching, (4) fixation and (5) washing, the process step (3) with the process step (2) or process steps (2) and (4) can be combined to one process step, characterized in that one combines for process steps (1) and (2) or process steps (1) and (2) and (3) or combines process steps (1) and (2) and (3) and (4), to which the top layer of the material applies an amount of the corresponding processing liquid which is at most equivalent to the swelling volume of the material, the material is subjected to a heat treatment after each treatment with processing liquid, if necessary, water and dry.
  • the swelling volume of the material is to be understood as the volume of liquid that this material absorbs when it is immersed in water for at least 1 second.
  • the swelling volume depends on the layer thickness of the material in question, the degree of hardening of the binder in the layers and other layer additives such as those e.g. in Research Disclosure 17643, 1978, Sections IX B and XII A and in particular the addition of the highly swellable polymers according to DE 3,546,164. In general, it is 2 to 5 times the volume of the layer package in the dry state.
  • the size of the swelling volume can be regulated without impairing the photographic properties of the material.
  • the swelling volume of a material can be determined, for example, in a simple manner by weighing the material before and after immersion in water.
  • the swelling volume is the maximum amount of processing liquid that can be applied to the material.
  • the minimum amount of processing liquid corresponds to that fraction of the swelling volume with which the intended processing stage can just be carried out. This minimum amount, which obviously also depends on the structure of the material to be processed, can easily be determined by routine tests.
  • the processing liquid is applied as a thin film only on the layer side of the material to be processed. This can be done according to known methods, e.g. by spraying or applying the liquid by means of rollers or thin slits along which the material is guided. These methods and other coating processes are e.g. in Photographic Science and Engineering, vol. 1, 1958, pages 156 to 160, and vol. 5, 1961, pages 48 to 54. Casting processes for the production of photographic elements, as described for example in Research Disclosure 17643, 1978, Section XV A, can also be used to apply the processing solutions. Spraying the solutions with nozzles, which are used in the inkjet printing process, has proven to be particularly advantageous.
  • wetting agents In order to achieve a homogeneous distribution of the small amount of liquid on the layer surface, it is generally necessary to add wetting agents to the processing liquids. Suitable for this are anionic or nonionic wetting agents, e.g. in Research Disclosure 17643, 1978, Section XI A. Fatty acid alkanolamides, alkylaryl polyether sulfates, polyethoxy compounds and perfluoro compounds such as are listed, for example, in DE 1,942,665 are particularly suitable.
  • the material After the application of the processing liquid, the material is subjected to a heat treatment until the corresponding processing step has ended.
  • a heat treatment for example, according to the in Journal of Scientific Instruments, Vol. 27, 1950, pages 170 to 171 and in The Engineer, 1955, pages 373 to 375 and 441 to 442 are followed, after which the material loaded with processing liquid is brought into contact with a heated plate.
  • temperatures for process step (1), it is generally sufficient to use temperatures of 30 to 70 ° C., preferably 30 to 60 ° C.
  • the required temperatures are between 30 and 120, in particular 50 and 120 and preferably between 60 and 90 ° C.
  • the duration of treatment is generally between 1 and 40 seconds.
  • the developer liquid to be used in process step (1) can detect the compositions customary for black and white developers, such as benzene compounds substituted with hydroxyl groups and / or (substituted) amino groups and (substituted) 1-phenylpyrazolidinones as developer substances, furthermore antioxidants such as sodium sulfite, antifoggants and clearing agents such as potassium bromide , Benzotriazole and mercaptobenzothiazole, silver complexing agents, organic solvents and wetting agents, etc.
  • Such compositions are described, for example, by G. Haist in Modern Photographic Processing, Vol. 1, John Wiley and Sons, NY, 1979, and LF Mason in Photographic Processing Chemistry, Focal Press, London, 1966, and further e.g. known from EP 14.688, DE 2.831.814, DE 2.640.659, EP 56.787, EP 44.813, EP 44.812, EP 23.888 and DE 1.180.788.
  • a hydroquinone-phenidone developer of the usual composition is preferably used in the process according to the invention, the hydroquinone concentration being between 15 and 35 g / l.
  • the pH of the developer liquid is preferably between 9.3 and 11.5.
  • the developer can contain 0.05 to 1% of a nonionic wetting agent, for example Emcol 5130 (Witco Chemical Corporation).
  • the concentrations of phenidone and benzotriazole in the developer are adjusted so that almost no development takes place at room temperature, i.e. no more than 10% of the amount of silver is developed within 30 seconds. This can prevent inhomogeneous development caused by uneven application of the developer liquid.
  • the exposed material is only developed after thermal activation by treating the material with developer liquid at preferably 30 to 70 ° C. for 1 to 20 seconds.
  • Particularly suitable concentrations of phenidone and benzotriazole are in the range from 0.1 to 0.6 and from 0.9 to 1.6 g / l.
  • the (weight) ratio of phenidone to bentriazole is preferably 1 to 4.
  • the bleaching liquid is applied to the developed material in accordance with process stage (2), or (2) combined with (3), or (2) combined with (3) and (4).
  • process stages as well as the compositions of the corresponding processing liquids are known from a large number of patents, e.g. from DE 2.037.684, DE 1.924.723, DE 2.258.076, DE 2.423.814, DE 2.448.433, DE 2. 651.969, DE 2.722.777, DE 2.722.776, DE 2.737.142, EP 34.793, EP 14,688, US 3,615,493, US 3,544,326, DE 2,600,966 and US 4,070,188.
  • the components available for the process steps mentioned include strong inorganic and organic acids, such as sulfuric acid, sulfamic acid, hydrobromic and hydroiodic acid, complexing agents such as iodides, bromides, mercapto compounds, rhodanides, thiourea, thiosulfates and sulfites, oxidizing agents such as quinones, azo compounds, heavy metal salts, Nitroso and nitrover bonds, color bleaching catalysts such as diazines, antioxidants such as reductones and ascorbic acid and bleaching accelerators such as quaternary ammonium salts and phosphines.
  • solvents such as propyl alcohol and ethylene glycol monomethyl ether, wetting agents, curing agents, UV absorbers and optical brighteners can be added as further customary additives.
  • a processing liquid which is composed similarly to the treatment baths described in DE 2,448,433 for the combined color and silver bleaching of silver color bleaching materials is preferably used for process step (2) according to the invention, the processing liquid preferably 5 to 30 g of water-soluble aromatic nitro compound, 15 to 40 g of iodide (as potassium iodide), 50 to 200 g of sulfuric acid or a suitable other (an) organic acid, 2 to 15 g of color bleach catalyst and 0.5 to 20 g of a nonionic wetting agent per kg.
  • iodide as potassium iodide
  • the material coated with a color bleaching liquid is then preferably heated to 50 to 120 ° C. for 1 to 40 seconds for color bleaching.
  • processing liquids which have the same composition as the processing liquids for process step (2). However, it is necessary to increase the potassium iodide content to 40 to 250 g per kg of processing liquid.
  • Processing liquids for process stage (2), (3) and (4) combined are described in DE 2,651,969.
  • a strong acid a water-soluble organic oxidizing agent and a color bleaching catalyst, they contain a water-soluble phosphine, preferably in an amount of 5 to 150 g per kg of processing liquid.
  • other ligands such as rhodanide, bromide, iodide and / or thiourea can also be present.
  • Processing liquids can also be used for the combined process stages (2) and (3) or (2), (3) and (4) which are free of iodide ions and instead contain bromide ions as complexing agents.
  • hydrobromic acid e.g. Processing fluids are simply composed, since hydrobromic acid simultaneously provides protons and complexing agents.
  • Such processing liquids then contain only hydrobromic acid, color bleaching catalyst and nitro compound. These components are preferably present in concentrations of 100 to 350 g / kg hydrobromic acid (48%), 1 to 5 g / kg color bleach catalyst and 2 to 30 g / kg nitro compound.
  • the material treated in this way is finally watered in the usual way and then dried.
  • the process according to the invention can be used to process silver color bleaching materials, the carrier of which is virtually unable to absorb any processing liquids.
  • materials with supports made of polyester and possibly pigmented cellulose acetate are suitable.
  • Paper substrates should be coated on both sides with a lacquer or polymer layer.
  • a large number of patent specifications provide information about the many possibilities for arranging various photographic layers on the supports mentioned. Examples include DE 1.938.823, DE 1.938.768, DE 2.121.175, DE 2.121.176, DE 2.132.836, DE 2.132.835, DE 2.147.560, DE 2.216.592, DE 2.216.620, DE 2.223 .311, DE 2,547,720, DE 2,831,814 and EP 39,313.
  • a photographic material for the silver bleaching process is produced.
  • the following layers are applied to a polyethylene-coated paper backing: a gelatin infusion from 1.2 gm ⁇ 2 gelatin, a red-sensitive layer containing 1.0 g gelatin, 0.47 g silver as silver bromoiodide emulsion with 2.6 mol% iodide and 155 mg of the blue-green image dye of the formula (100) per m2 contains an intermediate gelatin layer of 1.5 gm ⁇ 2 gelatin, a green-sensitive layer containing 1.4 g gelatin, 0.24 g silver as a silver bromoiodide emulsion with 2.6 mol% iodide and 165 mg of the purple image dye of the formula ( 101) contains, a filter yellow layer of 1.6 gm ⁇ 2 gelatin, 0.04 gm ⁇ 2 colloidal silver and 0.054 gm ⁇ 2 of the yellow dye of the formula (102) a blue-sensitive layer containing 0.9 g of gelatin, 0.22 g of silver
  • the material is exposed behind a step wedge with an illuminance of 50 lux for 1.5 seconds. Then, at room temperature, 24 ml of developer per m2 of carrier area is applied evenly to the layer side of the material with a "K" control coater (R.K. Print-Coat Instruments, Lillington, Roystone, UK) and heated on a hot plate at 35 ° C for 10 seconds.
  • K control coater
  • the developer has the following composition: Diethyl triaminopentasodium acetate (40%) 20.6 g Potassium hydroxide 31.0 g Potassium metabisulfite 25.5 g Sodium sulfite 14.7 g Boric acid 15.7 g Potassium bromide 2.0 g Ascorbic acid 9.8 g Diethylene glycol monoethyl ether 49.0 g Hydroquinone 29.4 g Phenidon Z 2.9 g Benzotriazole 0.9 g Emcol 5130 (3%) 15.3 g Water up to 1000 ml
  • the bleach bath has the following composition: m-nitrobenzenesulfonic acid (sodium salt) 19.3 g Sulfuric acid (conc.) 165.4 g Potassium iodide 29.6 g Adduct of 35 moles of ethylene oxide with 1 mole of octadecyl alcohol 11.5 g 2,3,6-trimethylquinoxaline 8.9 g 3-mercaptopropanesulfonic acid (sodium salt) 17.1 g Acetic acid (100%) 41.9 g Water up to 1000 g
  • Silver development and color bleaching is now complete.
  • the material still contains excess silver and silver halide, which can be removed in a conventional manner with known silver bleaching and fixing baths, for example by exposure to a silver bleach bath for one minute, per liter of solution 18 g CuSO4 ⁇ 5H2O 20 g KBr 150 ml HCl (conc.) contains, and then fixation in a fixer that per liter of solution 200 g ammonium thiosulfate and 24 g ammonium bisulfite and 39 g ammonium sulfite contains.
  • Figure 1 shows the measured integral reflectance densities as a function of the logarithm of the exposure for the three color channels red, green and blue.
  • Example 1 The material described in Example 1 is exposed and developed as indicated there. After development, 24 ml of a combined silver color bleaching bath (temperature 20 ° C.) per m2 are applied uniformly to the layer side of the material in the manner given in Example 1 and brought into contact with a heating plate at a temperature of 90 ° for 5 seconds.
  • a combined silver color bleaching bath temperature 20 ° C.
  • the silver color bleach bath has the following composition: m-nitrobenzenesulfonic acid (sodium salt) 19.3 g Sulfuric acid (conc.) 165.4 g Potassium iodide 101.0 g Adduct of 35 moles of ethylene oxide with 1 mole of octadecyl alcohol 11.5 g 2,3,6-trimethylquinoxaline 8.9 g 3-mercaptopropanesulfonic acid (sodium salt) 17.1 g Acetic acid (100%) 41.9 g Water up to 1000 g
  • Example 1 The material described in Example 1 is first treated as in Example 2. After the silver color bleaching, 63 ml of fixing solution with the following composition: Ammonium thiosulfate 200 g Ammonium bisulfite 12 g Ammonium sulfite 39 g Water up to 1000 g applied per m2 of material. Allow to act for 30 seconds at room temperature. Then another 31 ml of this fixing solution per m2 of material are applied. After a further 30 seconds of exposure at room temperature, watering and drying are carried out in the usual way. A result similar to that described in Example 1 is obtained.
  • Example 1 The material described in Example 1 is exposed and developed as indicated there. After development, 24 ml of a combined silver color bleach-fixer (temperature 20 ° C) per m2 applied evenly to the layer side of the material in the manner indicated in Example 1 and heated on a hot plate at 120 ° C. for 10 seconds.
  • the combined silver color bleach-fixer has the following composition: m-nitrobenzenesulfonic acid (Na salt) 19.3 g Sulfuric acid conc.
  • the material After the combined silver color bleaching fixation, the material is watered and dried in a conventional manner. A positive image of the exposed gray wedge with properties similar to those described in Example 1 is obtained.
  • the exposed material according to Example 1 is only developed after thermal activation.
  • Phenidon Z 0.3 g per liter Benztriazole 1.2 g per liter
  • Example 1 Development takes place on a hot plate at 60 ° C for 5 seconds. After color bleaching, silver bleaching, fixing, washing and drying as in Example 1, a positive image of the exposed gray wedge with properties similar to those described in Example 1 is obtained.
  • the photographic silver color bleaching material described in Example 1 is exposed behind a step wedge, developed in a conventional black and white developer at 30 ° C. for 1 minute, watered and dried for 2 minutes.
  • the developer has the composition: Ethylenediaminetetrasodium acetate 2 g Potassium sulfite 37 g Sodium sulfite 15 g Phenidon Z 3 g Hydroquinone 15 g Potassium metaborate 11 g Boric acid 7.7 g Ascorbic acid 12.3 g Potassium bromide 2 g Benzotriazole 0.9 g Water up to 1000 ml
  • Example 2 As in Example 1, 24 ml per m2 of a bleaching bath (temperature 20 ° C.) of the following composition are applied to the layer side of the material treated in this way: Hydrobromic acid (48%) 337 g 2,3,6-trimethylquinoxaline 1.5 g m-nitrobenzenesulfonic acid (Na salt) 2.0 g Adduct of 35 moles of ethylene oxide with 1 mole of octadecyl alcohol 2.0 g Water up to 1000 ml
  • the mixture is then heated on a hot plate at 70 ° C. for 5 seconds and then fixed and watered in a conventional manner.
  • a positive image of the exposed gray wedge is obtained with a good contrast balance and a very good minimum density.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP87810786A 1987-01-06 1987-12-31 Process for treating exposed photographic silver dyebleaching materials Pending EP0274357A3 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH22/87 1987-01-06
CH2287 1987-01-06
CH161587 1987-04-28
CH1615/87 1987-04-28

Publications (2)

Publication Number Publication Date
EP0274357A2 true EP0274357A2 (fr) 1988-07-13
EP0274357A3 EP0274357A3 (en) 1989-09-20

Family

ID=25683281

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87810786A Pending EP0274357A3 (en) 1987-01-06 1987-12-31 Process for treating exposed photographic silver dyebleaching materials

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US (1) US4868098A (fr)
EP (1) EP0274357A3 (fr)
CN (1) CN87105999A (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0603805A3 (fr) * 1992-12-21 1995-08-02 Eastman Kodak Co Régulation de la diffusion d'un développement dans les éléments photographiques.

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USH1263H (en) 1989-02-07 1993-12-07 Konica Corporation Image forming method and apparatus
US5114836A (en) * 1989-02-07 1992-05-19 Konica Corporation Method of development comprising intermittently spraying a photographic material
JPH03174151A (ja) * 1989-09-07 1991-07-29 Fuji Photo Film Co Ltd カラー画像形成方法
FI923023A7 (fi) * 1990-10-31 1992-06-29 Baxter Int Lähellään tapahtuvan verisuonittumisen aikaansaava istutemateriaali
US5262285A (en) * 1992-05-04 1993-11-16 Eastman Kodak Company Methods and compositions for retouching film images
US6113288A (en) * 1996-06-14 2000-09-05 Eastman Kodak Company Water deposition apparatus and method
US5708904A (en) * 1996-06-14 1998-01-13 Eastman Kodak Company Photographic emulsion surface reforming method
US5702875A (en) * 1996-06-28 1997-12-30 Eastman Kodak Company Weakly alkaline ascorbic acid developing composition, processing kit and method using same
CN106842809A (zh) * 2015-12-07 2017-06-13 蔡元 古典印相中的“留白”式印相方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3230089A (en) * 1962-02-21 1966-01-18 Bell & Howell Co Rapid photographic developing
US3620725A (en) * 1969-01-23 1971-11-16 Technology Inc Rapid photographic development system
CH576158A5 (fr) * 1972-02-28 1976-05-31 Ciba Geigy Ag
CH584914A5 (fr) * 1973-10-12 1977-02-15 Ciba Geigy Ag
JPS51121331A (en) * 1975-04-16 1976-10-23 Fuji Photo Film Co Ltd Silver dye bleaching process
CH597627A5 (fr) * 1975-11-17 1978-04-14 Ciba Geigy Ag
CH633641A5 (de) * 1977-07-21 1982-12-15 Ciba Geigy Ag Verfahren zur herstellung maskierter positiver farbbilder nach dem silberfarbbleichverfahren.
CH656725A5 (de) * 1983-01-26 1986-07-15 Ciba Geigy Ag Photographisches material fuer silberfarbbleichverfahren.
CH657710A5 (de) * 1983-07-20 1986-09-15 Ciba Geigy Ag Verfahren zur verarbeitung photographischer silberfarbbleichmaterialien.
EP0149978A3 (en) * 1984-01-20 1988-08-31 Ciba-Geigy Ag Process for the production of photographic images by the silver dye-bleaching process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0603805A3 (fr) * 1992-12-21 1995-08-02 Eastman Kodak Co Régulation de la diffusion d'un développement dans les éléments photographiques.

Also Published As

Publication number Publication date
US4868098A (en) 1989-09-19
EP0274357A3 (en) 1989-09-20
CN87105999A (zh) 1988-07-20

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