EP0286593A2 - Procédé pour former des images colorées positives pour masque suivant le procédé de blanchiment des couleurs à l'argent - Google Patents

Procédé pour former des images colorées positives pour masque suivant le procédé de blanchiment des couleurs à l'argent Download PDF

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Publication number
EP0286593A2
EP0286593A2 EP88810206A EP88810206A EP0286593A2 EP 0286593 A2 EP0286593 A2 EP 0286593A2 EP 88810206 A EP88810206 A EP 88810206A EP 88810206 A EP88810206 A EP 88810206A EP 0286593 A2 EP0286593 A2 EP 0286593A2
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EP
European Patent Office
Prior art keywords
silver
layer
dye
iodide
mol
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Withdrawn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
EP88810206A
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German (de)
English (en)
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EP0286593A3 (en
Inventor
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 EP0286593A2 publication Critical patent/EP0286593A2/fr
Publication of EP0286593A3 publication Critical patent/EP0286593A3/de
Withdrawn legal-status Critical Current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
    • 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
    • G03C7/18—Processes for the correction of the colour image in subtractive colour photography

Definitions

  • the present invention relates to a method for producing masked positive color images by the silver color bleaching method.
  • Such a method is already known from DE-A-25 47 720.
  • This method is based on assigning a iodide-free or low-iodide silver halide emulsion in a silver color bleaching material with several color layers absorbing in different spectral ranges, the main color density of which corresponds to a secondary absorption to be corrected in another layer, and a layer with colloidal in its immediate vicinity arranges nuclei suitable for physical silver development, while at the same time those iodide-containing silver halide emulsions are assigned to those color layers whose undesired secondary absorption is to be masked.
  • This method can be further improved according to the teaching given in DE-A-2 831 814 by adding a relatively insensitive, iodide-free silver halide emulsion and, if appropriate, a development inhibitor to the layer which contains the colloidal nuclei.
  • developer solutions containing such complexing agents have the disadvantage that the soluble silver complexes which accumulate therein during the development of the exposed materials are not stable under the prevailing reducing conditions. These silver complexes are gradually reduced to metallic silver, which is deposited in the form of an annoying silver sludge. This silver sludge can adhere to the photographic materials to be developed and produce stains therein or settle on parts of the processing system, which is a great disadvantage, particularly in the case of continuously operating systems.
  • the object of the present invention is therefore to modify the development step described in the processes according to DE-A-2 547 720 and 2 831 814 in such a way that the formation of the silver sludge in the developer solution does not occur.
  • bromides are used in high concentration as silver complexing agents in the developer solution.
  • the present invention furthermore relates to the developer solution which can be used in the process according to the invention and contains 0.3 to 1.0 mol / l of a bromide.
  • a substance which is assigned to another is understood here to mean those which belong to the same layer or two adjacent layers of a photographic silver color bleaching material and can interact with one another.
  • a number of different masking effects can be achieved using the described method.
  • one or two secondary color densities are compensated for by an image dye or that one secondary color density is compensated for each of two image dyes.
  • iodide-free and one iodide-containing emulsion layer are combined with only one seed layer in such a way that only one secondary color density is compensated for from each color layer.
  • the spectral sensitivity of the silver halide emulsions preferably coincides with the main absorption maximum of the image dye to which they are assigned.
  • the general case is that in which the dye and the associated emulsion sensitized to the complementary color of the base color are in the same layer.
  • these related components can also be at least partially in a layer adjacent to the dye layer.
  • Such layer arrangements are e.g. in DE-A-2 036 918, 2 132 835 and 2 132 836. They primarily serve to influence the relatively steep gradation in silver color bleaching materials or to increase the sensitivity.
  • the layer that contains the dye whose main color density corresponds to a secondary color density to be masked as can already be seen from the description of the material above:
  • the iodide-free silver halide emulsion belonging to this dye must be in the layer itself, i.e. as close as possible to the associated dye.
  • This additional emulsion layer is preferably also iodide-free or, if desired, can also contain a small amount of iodide ions, as a result of which the strength of the desired masking effect can be controlled. It is also possible to select spectral sensitivities other than those in the respective complementary color for the emulsions assigned to the individual dye layers. Such variants, suitable for the construction of so-called false color films, are e.g. in DE-A-2 132 835.
  • Silver color bleaching materials for reproducing colored originals are generally trichromatic and contain three layers of color, one each in the subtractive basic colors yellow, purple and teal. To achieve special effects, materials with other colors or with only two layers of color can also be used. in the Otherwise, the yellow, purple and cyan dyes known per se for this purpose can be used as image dyes in combination with the appropriate spectral sensitizers.
  • silver halide emulsions those are normally used which contain silver chloride, bromide or iodide or mixtures of these halides.
  • Silver halide emulsions containing iodide normally contain between 0.1 and 10 mole percent silver iodide, the rest being silver chloride and / or bromide (e.g. 0 to 99.9 mole percent silver chloride and 0 to 99.9 mole percent silver bromide).
  • Iodide-free silver halide emulsions preferably contain silver chloride, silver bromide or a silver chloride-silver bromide mixture. The iodide-free silver halide emulsions of the seed layer are not sensitized.
  • Gelatin is usually used as a protective colloid to prepare these emulsions; however, other water-soluble protective colloids such as polyvinyl alcohol or polyvinyl pyrrolidone, etc. can also be used; furthermore, part of the gelatin can be replaced by dispersions of non-water-soluble high-molecular substances. Common is e.g. the use of dispersion polymers of ⁇ , ⁇ -unsaturated compounds such as acrylic esters, vinyl esters and ethers, vinyl chloride, vinylidene chloride and other mixtures and copolymers.
  • Suitable colloidal nuclei for the deposition of metallic silver from silver complex compounds are, for example, colloidal hydrosols made of noble metals such as gold, silver or palladium, and also metal sulfides such as nickel or silver sulfide. Since these germs only have to be introduced in very small amounts, for example 1 mg to 200 mg per m2, there is generally no risk of interference due to light absorption or scattering. However, those germs are preferably introduced into the layer which can be removed later, for example during the processing process. A hydrosol made of colloidal silver is particularly suitable for this, which can be effortlessly removed from the material again in the silver bleaching process can.
  • the yellow silver hydrosol which can be installed directly below the yellow dye layer in a yellow filter layer intended to absorb the blue radiation, is particularly suitable.
  • Such a release layer generally consists of pure binder, e.g. Gelatin, and contains neither dye nor silver halide emulsion. If it is favorable for the overall layer structure, it can also e.g.
  • the separating layer can contain other additives, such as substances that inhibit color bleaching, additional binders, such as contain water-soluble colloids or water-insoluble dispersion polymers, furthermore the additives customary for the construction of photographic layers, such as plasticizers, wetting agents, light stabilizers, filter dyes or curing agents.
  • Suitable development inhibitors are the sulfur-containing compounds known as antifoggants from one of the following classes: aliphatic sulfur compounds, mercaptothiazolium salts, mercaptotriazolium salts, mercaptotetraazaindenes, mercaptotetrazoles and optionally other compounds whose silver salts have a solubility between that of silver bromide and silver sulfide.
  • These development inhibitors are bound to the particles of the unsensitized, iodide-free silver halide emulsion of layer (c) by diffusion-resistant adsorption.
  • the following compounds are particularly suitable as stabilizing agents: cysteine, 2-mercaptobenzothiazole, N-methylmercaptotriazole, phenylmercaptotetrazole, the latter being preferred.
  • a fine-grained emulsion consisting of silver chloride, silver bromide or silver chlorobromide can be used as the insensitive emulsion, which is generally not spectrally sensitized and is so insensitive that upon exposure, under which the light-sensitive emulsions of the other layers exposed to saturation, there are no developable grains that could interfere with image formation.
  • the proportion of silver chloride is about 10-90 mol%, preferably 30-70 mol%, and the emulsion should preferably also be iodide-free.
  • the average grain diameter is generally approximately 0.05 ⁇ m to 1.2 ⁇ m, preferably 0.4 ⁇ m to 0.8 ⁇ m.
  • the exposed silver halide layers are developed in the presence of bromide as a silver complexing agent, i.e. of an anion which is capable of forming water-soluble, diffusible complexes with silver ions.
  • a silver complexing agent i.e. of an anion which is capable of forming water-soluble, diffusible complexes with silver ions.
  • One liter of developer solution should contain between 0.3 and 1.0 mole of a bromide, preferably an inorganic bromide such as e.g. Contain sodium, potassium and ammonium bromide, the optimum amount depending on the nature of the material, the temperature of the developing bath and the desired exposure time can vary within the specified limits.
  • a particularly favorable concentration range is between 0.50 and 0.75 mol / l. Potassium bromide is preferably used.
  • a silver dye bleaching material suitable for making positive overlay copies of a positive original is made in the following manner:
  • the material also contains 0.48 g / m2 of the curing agent 2-amino-4-hydroxy-6- (4-methylmorpholinium) -1,3,5-triazine tetrafluoroborate.
  • the material is exposed behind a gray wedge individually with an additive color filter blue, green or red, and in one case with all three filters (blue + green + red).
  • the exposure times are set so that in the superposition (blue + green + red) a gray wedge is created which is as neutral as possible after processing.
  • the temperature of the processing baths is 30 ° C.
  • the developer bath contains the following components per liter of solution: Ethylene diamine tetraacetic acid sodium salt 4.0 g Potassium sulfite 19.9 g Sodium sulfite 38.0 g Lithium sulfite 0.6 g Hydroquinone 8.0 g Phenidon Z 0.5 g Potassium carbonate 19.5 g Potassium bicarbonate 13.3 g Benzotriazole 1.0 g Potassium bromide 40.0 g (0.33 m)
  • the bleaching bath has the following composition per liter of solution: Sulfuric acid (100%) 41.8 g m-Nitrobenzenesulfonic acid sodium salt 7.5 g Potassium iodide 9.0 g 2,3,4-trimethylquinoxaline 1.1 g Bis-cyanoethyl-sulfoethyl-phosphine, potassium salt 2.9 g
  • the fixer contains per liter of solution: Ammonium thiosulfate 200.0 g Ammonium bisulfite 6.9 g Ammonium sulfite 17.9 g
  • the color densities of the four wedges obtained are measured with a densitometer and from this the analytical color densities of the three color channels cyan (C) magenta (M) and yellow (Y) calculated.
  • the color density curves of the various wedges thus obtained are recorded in FIGS. 1A to 1D, the density of the exposed gray wedge on the abscissa and the color densities in "Unity neutral normalized analytical densities" (UNNAD) on the ordinate, cf. AJSant, Phot.Sci.Eng. 14.356 (1970).
  • the masking effect can be expressed as the difference between the sensitivity of the yellow layer when exposed to gray (blue + green + red) and the sensitivity of the yellow layer when exposed to blue alone. It is 0.13 log. Units at UNNAD 0.4.
  • Example 1 The material according to Example 1 is exposed and processed as described there, with the exception that the developer solution contains 60 g of potassium bromide per liter (0.50 m / l). The difference between the sensitivity of the yellow layer when exposed to gray and the sensitivity of the yellow layer when exposed to blue alone is 0.24 log. Units at UNNAD 0.4.
  • Example 1 The material according to Example 1 is exposed and processed as described there, with the exception that the developer solution contains 80 g of potassium bromide per liter (0.67 m / l). The difference between the sensitivity of the yellow layer when exposed to gray and the sensitivity of the yellow layer when exposed to blue alone is 0.31 log. Units at UNNAD 0.4.
  • Example 1 The material according to Example 1 is exposed and processed as described there, with the exception that the developer solution contains 100 g of potassium bromide per liter (0.84 m / l). The differences The limit between the sensitivity of the yellow layer when exposed to gray and the sensitivity of the yellow layer when exposed to blue alone is 0.25 log. Units at UNNAD 0.4.
  • Example 1 If the material according to Example 1 is treated with the developer solutions described in DE-A-2 547 720 and 2 831 814 and additionally contain 2.0 g / l potassium bromide, the masking effect obtained is the same as in Example 3, but must accept all the disadvantages associated with the formation of silver sludge.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP88810206A 1987-04-06 1988-03-28 Process for producing colour-positive masked images according to the silver dye-bleaching process Withdrawn EP0286593A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1313/87 1987-04-06
CH131387 1987-04-06

Publications (2)

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EP0286593A2 true EP0286593A2 (fr) 1988-10-12
EP0286593A3 EP0286593A3 (en) 1989-09-06

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP88810206A Withdrawn EP0286593A3 (en) 1987-04-06 1988-03-28 Process for producing colour-positive masked images according to the silver dye-bleaching process

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US (1) US4879203A (fr)
EP (1) EP0286593A3 (fr)
JP (1) JPS63261261A (fr)
CN (1) CN88101946A (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2289937A1 (fr) * 1974-10-28 1976-05-28 Ciba Geigy Ag Procede pour former des images positives masquees en couleurs selon le procede de decoloration a l'argent
FR2398327A1 (fr) * 1977-07-21 1979-02-16 Ciba Geigy Ag Procede pour former des images en couleurs, positives, masquees, selon le procede de blanchiment des couleurs a l'argent, et materiau photographique utilise a cet effet

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2507154A (en) * 1947-10-17 1950-05-09 Eastman Kodak Co Direct positive photographs using color developers
BE636671A (fr) * 1960-05-13
CH526134A (de) * 1969-07-25 1972-07-31 Ciba Geigy Ag Verfahren zur Herstellung eines photographischen Farbbildes nach dem Silberfarbbleichverfahren
CH542462A (de) * 1970-07-07 1973-09-30 Ciba Geigy Ag Verfahren zur Herstellung eines photographischen Farbbildes nach dem Silberfarbbleichverfahren
CH550423A (de) * 1970-07-07 1974-06-14 Ciba Geigy Ag Verfahren zur herstellung eines photographischen farbbildes nach dem silberfarbbleichverfahren.
FR2275801A1 (fr) * 1974-06-03 1976-01-16 Eastman Kodak Co Procede photographique de blanchiment de colorants par l'argent
JPS55138742A (en) * 1979-04-17 1980-10-29 Fuji Photo Film Co Ltd Silver halide emulsion developing method
US4368256A (en) * 1980-07-22 1983-01-11 Ciba-Geigy Ag Process for production of masked positive color images by the silver dye bleach process and the silver dye bleach material used in this process
JPS5811937A (ja) * 1981-07-15 1983-01-22 Fuji Photo Film Co Ltd 銀染料漂白処理方法
JPS5870223A (ja) * 1981-10-22 1983-04-26 Konishiroku Photo Ind Co Ltd 直接ポジ画像形成方法
IT1196194B (it) * 1984-07-20 1988-11-10 Minnesota Mining & Mfg Procedimento per formare immagini positive dirette,elementi agli alogenura d'argento positivi diretti,composizioni e composti come specialita' caratteristiche di deti procedimenti e elementi
US4661437A (en) * 1984-07-27 1987-04-28 Ciba-Geigy Ag Photographic material with heterocylic azo dye for the silver dye bleach process
EP2289937A1 (fr) * 2009-08-24 2011-03-02 Wilfried Stücker Production d'anticorps monoclonaux in vitro

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2289937A1 (fr) * 1974-10-28 1976-05-28 Ciba Geigy Ag Procede pour former des images positives masquees en couleurs selon le procede de decoloration a l'argent
FR2398327A1 (fr) * 1977-07-21 1979-02-16 Ciba Geigy Ag Procede pour former des images en couleurs, positives, masquees, selon le procede de blanchiment des couleurs a l'argent, et materiau photographique utilise a cet effet

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 86, Nr. 22, 30. Mai 1977, Seite 545, Zusammenfassung Nr. 163542t, Columbus, Ohio, US; N.R. NOVIKOVA et al.: "Effect of antilogging substances on the size and structure of developed image silver in autoradiographic emulsions", & ZH. NAUCHN. PRIKL. FOTOGR. KINEMATOGR. 1977, 22(1), 10-14 *
RESEARCH DISCLOSURE, Nr. 151, November 1976, Seiten 11-13, Zusammenfassung Nr. 15107, Industrial Opportunities Ltd, Havant, Hampshire, GB; R.A. HALE et al.: "Bleaching solutions" *

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Publication number Publication date
US4879203A (en) 1989-11-07
JPS63261261A (ja) 1988-10-27
EP0286593A3 (en) 1989-09-06
CN88101946A (zh) 1988-10-26

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