EP0018530A2 - Procédé d'obtention d'images photographiques en couleurs - Google Patents

Procédé d'obtention d'images photographiques en couleurs Download PDF

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Publication number
EP0018530A2
EP0018530A2 EP80101980A EP80101980A EP0018530A2 EP 0018530 A2 EP0018530 A2 EP 0018530A2 EP 80101980 A EP80101980 A EP 80101980A EP 80101980 A EP80101980 A EP 80101980A EP 0018530 A2 EP0018530 A2 EP 0018530A2
Authority
EP
European Patent Office
Prior art keywords
developer
color
bromide
development
layer
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
EP80101980A
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German (de)
English (en)
Other versions
EP0018530B1 (fr
EP0018530A3 (en
Inventor
Ubbo Dr. Wernicke
Heinz Dr. Meckl
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.)
Agfa Gevaert AG
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Agfa Gevaert AG
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Filing date
Publication date
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0018530A2 publication Critical patent/EP0018530A2/fr
Publication of EP0018530A3 publication Critical patent/EP0018530A3/de
Application granted granted Critical
Publication of EP0018530B1 publication Critical patent/EP0018530B1/fr
Expired legal-status Critical Current

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Classifications

    • 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
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/44—Regeneration; Replenishers

Definitions

  • the invention relates to an improved method for producing photographic images.
  • the invention relates to an improved reversal process for producing color photographic images with materials containing at least one silver halide emulsion layer.
  • the bromide ion concentration is therefore not more than 0.6-1.5 g KBr per liter. ' It is necessary to keep the selected bromide ion concentration constant in the course of the development process (J.H. PRIESTHOFF, Journal of the SMPTE, 65 (1956) 473).
  • GB-PS 835,556 It is also known from GB-PS 835,556 to use ion exchangers for processing developers. These remove the disruptive halide ions from the developer, so that a used developer treated with the ion exchanger can be used again as the basis for a regenerator.
  • a disadvantage of the process known from GB-PS 835,556, however, is that under the specified conditions relatively little bromide ions are bound by the ion exchanger. In order to absorb the relatively high amounts of halide released from the photographic material during development, high amounts of ion exchangers must therefore be used, which have to be reprocessed in a complicated process for economic reasons.
  • Another disadvantage of the method is that - especially with larger amounts of ion exchangers - it is noticeable that these ion exchangers also bind the developer substances contained in the developer themselves. In addition to the loss of developer substance, this also leads to a continuous change in the absorption capacity of the ion exchanger for halide ions and consequently to a variable bromide ion content in the treated developer. This makes ongoing analytical checks and corrections necessary.
  • Suitable bromide ion concentrations have at least 3 g KBR per liter, preferably at least 6 g KBr per liter and in a particularly preferred embodiment at least 10 g KBr per liter.
  • the bromides are generally used in the form of alkali metal bromides.
  • the equilibrium concentrations of bromide mentioned may be significantly lower, but are still at least twice or three times the usual concentrations.
  • the methods used to regulate the bromide ion concentration correspond to those known per se.
  • membrane separation processes can be used.
  • the process according to the invention is applicable to the treatment of a light-sensitive photographic material which contains couplers.
  • couplers These compounds can be the usual color couplers, which are usually incorporated into the silver halide layers themselves.
  • the red-sensitive layer contains a non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or ⁇ -naphthol type.
  • the green-sensitive layer contains at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or indazolone type usually being used.
  • the blue-sensitive layer unit contains at least one non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
  • Color couplers of these types are known in large numbers and are described in a large number of patents.
  • An example here is the publication "Color Coupler” by W. PELZ in "Messages from the Research Laboratories of Agfa, Leverkusen / Kunststoff", Volume III (1961) and
  • 2-equivalent couplers can be used as non-diffusing color couplers; these contain a removable substituent in the coupling site, so that they only require two equivalents of silver halide to form the color, in contrast to the usual 4-equivalent couplers
  • the 2-equivalent couplers which can be used include, for example, the known DIR couplers, in which the cleavable residue is released as a diffusing development inhibitor after reaction with color developer oxidation products.
  • the so-called white couplers can also be used to improve the properties of the photographic material.
  • the non-diffusing color couplers and coloring compounds are added to the light-sensitive silver halide emulsions or other casting solutions by customary known methods. If the compounds are soluble in water or alkali, they can be added to the emulsions in the form of aqueous solutions, optionally with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide.
  • non-diffusing color couplers and coloring compounds are water- or alkali-insoluble compounds
  • they can be emulsified in a known manner, for example by mixing a solution of these compounds in a low-boiling organic solvent directly with the silver halide emulsion or initially with an aqueous gelatin solution is, whereupon the organic solvent is removed in a conventional manner.
  • a gelatin emulsate of the respective compound thus obtained is then mixed with the silver halide emulsion.
  • coupler solvents or oil formers are additionally used to emulsify such hydrophobic compounds; these are generally higher-boiling organic compounds which include the non-diffusing compounds which split off in the silver halide emulsions and which release color couplers and development inhibitors in the form of oily droplets.
  • coupler solvents or oil formers are generally higher-boiling organic compounds which include the non-diffusing compounds which split off in the silver halide emulsions and which release color couplers and development inhibitors in the form of oily droplets.
  • the usual silver halide emulsions are suitable for the present invention.
  • these can contain silver chloride, silver bromide, silver iodide or mixtures thereof.
  • Gelatin is preferably used as the binder for the photographic layers.
  • this can be replaced in whole or in part by other natural or synthetic binders.
  • natural binders e.g. Alginic acid and its derivatives such as salts, esters or amides, cellulose derivatives such as carboxymethyl cellulose, alkyl cellulose such as hydroxyethyl cellulose, starch or their derivatives such as ethers or esters or caragenates are suitable.
  • Synthetic binders include polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and the like.
  • the emulsions can also be chemically sensitized, e.g. by adding sulfur-containing compounds during chemical ripening, for example allyl isothiocyanate, allyl thiourea, sodium thiosulfate and the like.
  • Reducing agents e.g. the tin compounds described in Belgian patents 493,464 or 568,687, also polyamines such as diethylenetriamine, or aminomethanesulfinic acid derivatives, e.g. according to Belgian patent 547 323.
  • Precious metals such as gold, platinum, palladium, iridium, ruthenium or rhodium and compounds of these metals are also suitable as chemical sensitizers. This method of chemical sensitization is described in the article by R. KOSLOWSKY, Z.Wiss.Phot., 46, 65 - 72 (1951).
  • polyalkylene oxide derivatives for example with polyethylene oxide with a molecular weight between 1000 and 20,000.
  • condensation products of alkylene oxides and aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides have a molecular weight of at least 700, preferably more than 1000.
  • these sensitizers can of course be used in combination, as described in Belgian patent 537 278 and British patent 727 982.
  • the emulsions can also be spectrally sensitized, for example by the customary mono- or polymethine dyes, such as acidic or basic cyanines, hemicyanines, streptocyanines, merocyanines, oxonols, hemioxonols, styryl dyes or other, also trinuclear or polynuclear methine dyes, for example rhodacyanines or neocyanines.
  • the customary mono- or polymethine dyes such as acidic or basic cyanines, hemicyanines, streptocyanines, merocyanines, oxonols, hemioxonols, styryl dyes or other, also trinuclear or polynuclear methine dyes, for example rhodacyanines or neocyanines.
  • sensitizers are described, for example, in the work of FM HAMER "The Cy
  • the emulsions can contain the usual stabilizers such as, for example, homeopolar or salt-like compounds of mercury with aromatic or heterocyclic rings such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such compounds are described in the article by BIRR, Z.Wiss.Phot., 47, 2-58 (1952).
  • Other suitable stabilizers include heterocyclic mercapto compounds, for example phenyl mercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.
  • the emulsions can be hardened in the usual manner, for example with formaldehyde or halogen-substituted aldehydes which contain a carboxyl group such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes and the like.
  • the photographic layers can be hardened with hardeners of the epoxy type, the heterocyclic ethylene imine or the acryloyl type. Examples of such hardeners are e.g. in German Offenlegungsschrift 2,263,602 or in British Patent 1,266,655.
  • hardeners examples include diazine derivatives containing alkyl or arylsulfonyl groups, derivatives of hydrogenated diazines or triazines such as 1,3,5-hexahydrotriazine, fluorine-substituted diazine derivatives such as fluoropyrimidines, esters of 2-substituted 1,2-dihydroquinoline or 1, 2-dihydroisoquinoline-N-carboxylic acids.
  • vinyl sulfonic acid hardeners, carbodiimide or carbamoyl hardeners such as, for example, in German Offenlegungsschriften 2 263 602, 2 225 230 and 1 808 685 .
  • the French patent specification 1,491,807 the German patent specification 872,153 and the GDR patent specification 7218.
  • Other useful hardeners are described, for example, in British Patent 1,268,550.
  • the usual substrates are used. Suitable are e.g. Films made of cellulose nitrate, cellulose acetate such as cellulose triacetate, polystyrene, polyesters such as polyethylene terephthalate, polyolefins such as polyethylene or polypropylene, a baryted or a polyolefin-laminated, e.g. a polyethylene-laminated, paper base as well as glass and the like.
  • Suitable are e.g. Films made of cellulose nitrate, cellulose acetate such as cellulose triacetate, polystyrene, polyesters such as polyethylene terephthalate, polyolefins such as polyethylene or polypropylene, a baryted or a polyolefin-laminated, e.g. a polyethylene-laminated, paper base as well as glass and the like.
  • the process according to the invention is particularly suitable for the color development of photographic materials.
  • imagewise exposed photographic reversal material with at least one silver halide emulsion layer is subjected to black and white development and, if appropriate, further intermediate baths.
  • the photographic material is then veiled in a known manner and the photographic material treated in this way is developed in a second developer (color developer) to be used according to the invention to form a positive reversal image.
  • the advantage of the process according to the invention lies in the simple handling of regeneration of the developers used. This means that no complicated equipment is required to reprocess the used developers, and the increased absorption capacity of the ion exchangers means that only relatively small amounts of ion exchangers are required.
  • inventions are according to only about 1 kg of ion exchanger per 100 1 of developer is required, while for the removal of the same amount of bromide from a developer containing 2 g of potassium bromide per liter, under otherwise identical conditions, about 10 kg of ion exchanger are required.
  • a constant and reproducible developer composition is obtained by treating a used developer with small amounts of an ion exchanger, which developer composition can be reused as a regenerator after the addition of the necessary additional chemicals (rejuvenator).
  • Example 1 The procedure is as in Example 1, but a KBr content of 10 g per liter is specified in the color developer.
  • the KBr content in the filtrate after treatment with the anion exchanger is shown in Table 1.
  • a photographic material of the following structure is exposed imagewise in the usual way and subjected to the reverse processing indicated:
  • Layer 1 A blue-green layer containing a silver bromoiodide emulsion containing 7 mole% iodide prepared according Glafkides "Photographic Chemistry", Vol 1, page 289 ff, Fountain Press, London, 1958.
  • the silver content of the emulsion is - expressed in AgN0 3-100. g per kg of emulsion.
  • the emulsion is ripened in a known manner by adding sulfur compounds and gold I compounds. It is sensitized to the red spectral range and contains a color coupler with the following formula:
  • Layer 2 A second cyan layer containing a silver bromide iodide emulsion with 6 mol% iodide, produced by the process described under layer 1, but with a higher sensitivity.
  • the layer contains the same color coupler as layer 1.
  • Layer 3 A purple layer containing a silver bromide iodide emulsion as described under layer 1, but sensitized to the green spectral range. It contains a coupler of the following formula:
  • Layer 4 A second purple layer containing an emulsion as described under layer 2, but sensitized to the green spectral range and with the same coupler as layer 3.
  • Layer 5 A yellow filter layer made of a silver sol.
  • Layer 6 A yellow layer containing a silver bromide iodide emulsion with 4 mol% iodide, produced as described under layer 1, which is sensitive to the blue spectral range.
  • the layer contains a coupler of the following formula:
  • Layer 7 A further yellow layer containing a silver bromide iodide emulsion with 6 mol% iodide, produced as described under layer 1, but with a higher sensitivity in the blue spectral range than layer 6.
  • the layer contains the same color coupler as layer 6.
  • Layer 8 The structure is completed with a protective layer.
  • the casting solution used for this contains 1.6% gelatin in addition to the hardening and wetting agent. Order corresponding to 50 ml / sqm.
  • the imagewise exposed material is developed for 8 minutes at 30 ° C in the following first developer I.
  • the photographic material is then subjected to a stop bath, watered, exposed twice and developed in the developer II at 30 ° C. for 6 minutes.
  • Developer II corresponds to the developer specified in Example 1.
  • Developer II contains 10 g of potassium bromide
  • Second development time 10 minutes at 30 ° C.
  • Developer II contains 10 g of potassium bromide; Second development time: 6 minutes at 38 ° C.
  • Developer II contains 20 g of potassium bromide
  • Second development time 6 minutes at 38 ° C.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP80101980A 1979-04-26 1980-04-14 Procédé d'obtention d'images photographiques en couleurs Expired EP0018530B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792916836 DE2916836A1 (de) 1979-04-26 1979-04-26 Verfahren zur herstellung photographischer bilder
DE2916836 1979-04-26

Publications (3)

Publication Number Publication Date
EP0018530A2 true EP0018530A2 (fr) 1980-11-12
EP0018530A3 EP0018530A3 (en) 1981-11-25
EP0018530B1 EP0018530B1 (fr) 1984-02-29

Family

ID=6069274

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80101980A Expired EP0018530B1 (fr) 1979-04-26 1980-04-14 Procédé d'obtention d'images photographiques en couleurs

Country Status (4)

Country Link
US (1) US4348475A (fr)
EP (1) EP0018530B1 (fr)
JP (1) JPS55144240A (fr)
DE (2) DE2916836A1 (fr)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5895349A (ja) * 1981-11-30 1983-06-06 Fuji Photo Film Co Ltd 感光性プレ−トの現像補充液補充方法
US4546068A (en) * 1983-06-09 1985-10-08 Konishiroku Photo Industry Co., Ltd. Method for processing of light-sensitive silver halide color photographic material
JPS61231548A (ja) * 1985-04-05 1986-10-15 Konishiroku Photo Ind Co Ltd 写真廃液の処理方法及び写真自動現像機
JPS61251852A (ja) * 1985-04-30 1986-11-08 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
JPH07117701B2 (ja) * 1985-07-18 1995-12-18 富士写真フイルム株式会社 ハロゲン化銀感光材料およびその処理方法
US4813974A (en) * 1987-06-22 1989-03-21 Mobay Corporation Removal of excess halide ions in aqueous liquid formulations of basic dyestuffs
DE3800385A1 (de) * 1988-01-09 1989-07-20 Agfa Gevaert Ag Ueberlauffreies farbfotografisches entwicklungssystem
JP2670810B2 (ja) * 1988-07-07 1997-10-29 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
US4915137A (en) * 1988-08-15 1990-04-10 Hall James A Sheet plastic flange protector
JP2632035B2 (ja) * 1989-02-20 1997-07-16 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
JP2916539B2 (ja) * 1989-09-07 1999-07-05 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JP2630472B2 (ja) * 1989-10-30 1997-07-16 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JP2630473B2 (ja) * 1989-11-02 1997-07-16 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JP2673272B2 (ja) * 1989-11-17 1997-11-05 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
JPH04445A (ja) 1990-04-17 1992-01-06 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料の処理方法
GB9008750D0 (en) * 1990-04-18 1990-06-13 Kodak Ltd Method and apparatus for photographic processing solution replenishment
US5256525A (en) * 1991-12-19 1993-10-26 Eastman Kodak Company Blocked incorporated developers in a photographic element
US5344750A (en) * 1992-05-12 1994-09-06 Fuji Photo Film Co., Ltd. Color development processing method of silver halide color photographic material using a color developer where the color developing agent concentration and processing temperature are a function of bromide ion concentration
EP0752618A3 (fr) * 1995-06-12 1997-01-22 E.I. Du Pont De Nemours And Company Révélateur à base d'hydroquinone, procédé de recyclage de ce révélateur usagé et le révélateur recyclé
GB2306686A (en) * 1995-10-18 1997-05-07 Kodak Ltd Processing system for developing photographic materials

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE941340C (de) * 1950-07-11 1956-04-05 C Schleussner Fotowerke G M B Verfahren zur Farbentwicklung von diffusionsfeste Farbbildner enthaltenden lichtempfindlichen Filmen mit Hilfe von Farbentwicklern
GB835556A (en) * 1955-06-14 1960-05-25 Kodak Ltd Process for improving used photographic developing solutions
US3627530A (en) * 1969-07-18 1971-12-14 Du Pont Photographic developer solutions of high sulfite content and ph

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2073621A (en) * 1933-10-06 1937-03-16 Jesse M Blaney Method of removal of excess halides from photographic developing baths
GB709179A (en) * 1951-11-17 1954-05-19 Kodak Ltd Improvements in reconditioning used photographic developer solutions
GB1519105A (en) * 1975-12-02 1978-07-26 Fuji Photo Film Co Ltd Treating of photographic processing solutions
JPS5816172B2 (ja) * 1976-08-11 1983-03-30 富士写真フイルム株式会社 写真処理液中のカブリ成分の除去方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE941340C (de) * 1950-07-11 1956-04-05 C Schleussner Fotowerke G M B Verfahren zur Farbentwicklung von diffusionsfeste Farbbildner enthaltenden lichtempfindlichen Filmen mit Hilfe von Farbentwicklern
GB835556A (en) * 1955-06-14 1960-05-25 Kodak Ltd Process for improving used photographic developing solutions
US3627530A (en) * 1969-07-18 1971-12-14 Du Pont Photographic developer solutions of high sulfite content and ph

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SMPTE JOURNAL, Band 88, Nr. 3, Marz 1979 New York (US) J. WESLEY KLEPPE: "Practical Application of an Ion-Exchange Method for Color-Developer Reuse" Seiten 168-170 * das ganze Dokument * *

Also Published As

Publication number Publication date
EP0018530B1 (fr) 1984-02-29
DE2916836A1 (de) 1980-11-06
JPS6318730B2 (fr) 1988-04-20
DE3066734D1 (en) 1984-04-05
US4348475A (en) 1982-09-07
JPS55144240A (en) 1980-11-11
EP0018530A3 (en) 1981-11-25

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