EP0117227A2 - Matériel photographique pour le procédé de blanchiment des couleurs à l'argent - Google Patents

Matériel photographique pour le procédé de blanchiment des couleurs à l'argent Download PDF

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Publication number
EP0117227A2
EP0117227A2 EP84810036A EP84810036A EP0117227A2 EP 0117227 A2 EP0117227 A2 EP 0117227A2 EP 84810036 A EP84810036 A EP 84810036A EP 84810036 A EP84810036 A EP 84810036A EP 0117227 A2 EP0117227 A2 EP 0117227A2
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EP
European Patent Office
Prior art keywords
carbon atoms
formula
alkyl
substituted
radical
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
EP84810036A
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German (de)
English (en)
Other versions
EP0117227B1 (fr
EP0117227A3 (en
Inventor
Mario Dr. Fryberg
Heinrich Dr. Schaller
Rolf Dr. Steiger
Heinz Dr. Peter
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Cessione ilford AG
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Ciba Geigy AG
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Publication of EP0117227A2 publication Critical patent/EP0117227A2/fr
Publication of EP0117227A3 publication Critical patent/EP0117227A3/de
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Publication of EP0117227B1 publication Critical patent/EP0117227B1/fr
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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

Definitions

  • the present invention relates to photographic material for the silver color bleaching process, which contains at least one bleach inhibitor in at least one layer.
  • a negative silver image is first developed in the exposed material with a black and white developer.
  • the material is then bleached, whereby the silver of the silver image is oxidized (bleached) to a silver salt and at the same time the dye is reduced (bleached) according to the original silver image areas.
  • the silver salt still present is then removed by fixing and the material is washed.
  • One or more color bleaching catalysts are typically used for bleaching, e.g. Quinoxalines, pyrazines or phenazines, e.g. are described in DE-B-1547720 and DE-B-1547759.
  • Recording materials particularly suitable for the silver color bleaching process contain red, green and blue sensitive silver halide emulsion layers on a support which contain bleachable cyan (cyan) dyes, purple (magenta) dyes and yellow (yellow) dyes.
  • these dyes can also be accommodated in separate layers which are adjacent to the silver halide emulsion layers.
  • the bleach catalysts in the silver image areas are reduced.
  • the bleaching catalysts accelerate dye bleaching in the exposed areas.
  • the dye be bleached only in the silver image areas.
  • reduced bleaching catalysts also diffuse into adjacent layers and can cause bleaching of dyes there. This leads to an undesirable reduction in the dye density in this layer and ultimately to a color falsification in the color image.
  • nitro compounds are used as oxidizing agents in accordance with US Pat. No. 3,782,948.
  • the results achieved with these compounds are unsatisfactory.
  • the nitro compounds cannot be incorporated into the photographic layers in the desired distribution in all cases.
  • Binuclear heterocycles are used according to DE-A-2,949,167. However, these have the disadvantage that they adversely affect the kinetics of silver development.
  • the object of the present invention is now to prevent the undesired bleaching of image dyes by means of diffusing, reduced bleaching catalysts and at the same time the disadvantages to overcome as far as possible the previously proposed solutions.
  • the object is achieved according to the invention by incorporating 1,4-benzoquinones in silver color bleaching materials. These compounds are generally resistant to diffusion and are distinguished by a good bleach-inhibiting effect.
  • R is alkyl, preferably of the formula
  • Q is a group of the formula -OX, in which X has the meaning of R 5 - as defined above, but in particular alkyl with 3 or 4 carbon atoms or hydrogen, - or-COR 7 .
  • R is alkyl of preferably 1 to 20 carbon atoms. Suitable alkyl radicals are those as listed for R 4 , in particular those with 1 to 4 carbon atoms, methyl being particularly preferred.
  • R 7 is alkenyl, preferably having 3 to 20 carbon atoms. These alkenyl residues can be derived from the alkyl residues mentioned.
  • R 7 is above all cyclopentyl, cyclohexyl or cyclooctyl.
  • Suitable aralkyl groups R 7 which preferably contain 7 to 13 carbon atoms, are those as listed for R.
  • R 7 is also aryl preferably having 6 to 10 carbon atoms, for example phenyl and naphthyl.
  • the aryl groups are optionally substituted with 1 or 2 alkyl groups, preferably with (each) 1 to 4 carbon atoms.
  • Q is also a group of the formula -NR 8 R 9 , wherein R 8 is, in addition to hydrogen, alkyl having preferably 1 to 4 carbon atoms, such as Methyl, ethyl, propyl or butyl or isomers thereof, and R is hydrogen or alkyl having preferably 1 to 4 carbon atoms or a radical of the formula -COR 7 , in which R 7 has the meaning given.
  • R 8 and R9 together with the nitrogen atom to which they are attached can form a 5- or 6-membered ring which is optionally substituted with 1 or 2 alkyl groups, which preferably (each) contain 1 to 4 carbon atoms.
  • Preferred rings are, for example, pyrrolidinyl, piperidinyl or morpholinyl.
  • Q also represents a radical of the formula -P (O) (OR 10 ) ([O] x R 11 ), where x is 0 or 1.
  • R 10 and R 11 independently of one another denote hydrogen or alkyl having 1 to 20 carbon atoms, the alkyl radicals mentioned for R 4 being particularly suitable.
  • R 10 and R 11 can also form an alkylene chain which preferably contains 2 or 3 carbon atoms, which in turn can be substituted by one of the alkyl radicals mentioned having 1 to 20 carbon atoms.
  • R 10 is hydrogen or alkyl of I to 20 carbon atoms.
  • Suitable alkyl radicals R 10 are those as mentioned for R 4 .
  • R 11 is alkyl having 1 to 5 carbon atoms, the alkyl radicals preferably being unbranched.
  • Q is a group of formula -SO 2 R 12 wherein R such as chlorine, or 12 hydroxyl, halogen -NR 5 R 7, wherein R 5 and R 7 have The indicated meanings.
  • R 12 is hydroxyl
  • R is a radical of formula (2).
  • the compounds of formula (1) can also be in the form of salts.
  • Preferred compounds of formula (1) for use in silver color photographic bleaching processes are those in which R is in the 2- and R in the 5-position.
  • R in the compounds of formula (1) represents a radical of the formula wherein A is alkyl of 1 to 10 carbon atoms.
  • Q in the substituent R of the compound of the formula (1) is preferably -CO 2 R 4 , -OCOR 7 or cyano, where R 4 and R 7 have the meanings given to have.
  • R is a radical of the formula (2) in which Q-CO 2 R 4 in which R 4 is alkyl having 1 to 8 carbon atoms or cycloalkyl in the range of 5 to 8 carbon atoms, or -OCOR 7 in which R is alkyl having 1 to 4 carbon atoms
  • R 1 is a radical of the formula (2) in which Q has the meaning given
  • R 2 and R 3 are each methyl
  • p, q and k are each 1 and n is 1 to 10
  • Preferred alkoxy groups Q are those with 1 to 4 carbon atoms.
  • the quinones of formula (1) incorporated in silver color photographic bleaching material are good bleach inhibitors which are capable of reducing, i.e. active bleaching catalysts to oxidize.
  • the quinones are incorporated into the photographic material in a known manner in the form of dispersions or emulsions. In most cases they can be dispersed without high-boiling solvents such as di-n-butyl phthalate or tri-o-cresyl phosphate.
  • high-boiling solvents such as di-n-butyl phthalate or tri-o-cresyl phosphate.
  • quinone are dissolved in 10 ml ethyl acetate at about 40 ° C. This solution is added to a preferably likewise 40 ° C.
  • the amount of quinone depends on the type of photographic layer in which the compounds are to be incorporated. It can vary within wide limits. In general, 0.01 to 5 g per m 2 of quinone are introduced into the corresponding layer.
  • the effectiveness of the quinones according to the invention also depends on the particle size of the dispersion.
  • the quinones can, depending on the desired effect, all layers or only individual layers, for example silver halide emulsion, dye, silver halide emulsion dye, Intermediate or auxiliary layers can be added.
  • the quinones are preferably incorporated into the silver halide and dye-free intermediate gelatin layers in order to prevent diffusion of reduced bleach catalyst from one color layer to another.
  • 0.2 to 0.5 g quinone per m 2 layer area are generally sufficient to completely prevent bleach coupling between two color layers.
  • the quinones used according to the invention also allow the layer thickness of these intermediate gelatin layers to be reduced to a minimum.
  • the quinones of the formula (1) can also be used advantageously in filter and antihalation layers which contain colloidal particles of silver and in barrier layers which contain colloidal hydrosols or sulfides of noble or heavy metals.
  • the latent silver image created during exposure is developed.
  • the image dye assigned to the silver is bleached out in accordance with the image-based distribution of the silver.
  • the third step is necessary to reoxidize the excess image silver that is still present after the color bleaching.
  • the fourth step is now silver present entirely in the form of halides is removed by dissolving out with a complexing agent, in particular a salt of thiosulfuric acid, in order to make the finished image insensitive to further exposure and to clear the pure color image of cloudiness.
  • the second process step, color bleaching is carried out in the customary known processes in a strongly acidic medium, a catalyst being added to accelerate the color bleaching.
  • the bleaching baths also contain a silver complexing agent or ligand. Both components, catalyst and ligand, are necessary in order to transfer the reducing effect of the metallic, non-diffusible image silver to the likewise non-diffusible dye.
  • the reduced form of the catalyst resulting from reduction on the image silver serves as an intermediate support which, after covering a certain diffusion distance, irreversibly reduces the dye and thus bleaches, and is reoxidized itself to the original form.
  • the combined dye and silver bleach baths can contain alkyl or arylsulfonic acids and in particular p-toluenesulfonic acid, sulfuric acid, sulfamic acid or trichloroacetic acid. If appropriate, mixtures of these acids can also be used.
  • the pH of the bleaching bath is in particular not greater than 2 and preferably not greater than 1.
  • the water-soluble iodides are generally alkali metal iodides, especially sodium and potassium iodide.
  • oxidizing agent (component (c)) it is advantageous to use water-soluble aromatic mononitro and dinitro compounds, and also anthraquinone sulfonic acid derivatives, such as e.g. o- or m-nitrobenzenesulfonic acid or 2,4-dinitrobenzenesulfonic acid.
  • anthraquinone sulfonic acid derivatives such as e.g. o- or m-nitrobenzenesulfonic acid or 2,4-dinitrobenzenesulfonic acid.
  • the use of such oxidizing agents serves to influence the color balance and the contrast of the images produced in the color bleaching process and is known from DE 735 672, GB 539 190 and GB 539 509.
  • the compounds of component (c) serve to flatten the gradation.
  • Reductones or water-soluble mercapto compounds are advantageously used as antioxidants' component (d)).
  • Suitable reductones are, in particular, aci reductones with a 3-carbonylenediol (1,2) grouping, such as reductin, triose reductone or preferably ascorbic acid.
  • Examples of mercapto compounds are thioglycerol, but especially the compounds of the formula or preferably into consideration, in which q is an integer from 2 to 12, B is a sulfonic acid or carboxylic acid group and m is one of the numbers 3 and 4.
  • azines in particular derivatives of quinoxaline, are suitable as bleaching catalysts (c). These are e.g. in US-A-4,202,698.
  • Suitable bleach accelerators (f) are e.g. quaternary ammonium salts as are known from DE-A-2 139 401 and DE-A-2 716 136. These are preferably quaternary, optionally substituted piperidine, piperazine, pyrazine, quinoline, pyridine or tetraalkylammonium compounds and water-soluble tertiary phosphines as described in DE-A-2,651,169.
  • All baths can contain other common additives such as Contain hardening agents, wetting agents, optical brighteners or UV protection agents.
  • Baths of conventional composition can be used for silver development, e.g. those which contain hydroquinone as the developer and optionally additionally l-phenyl-3-pyrazolidinone. If necessary, the silver development bath already contains a bleaching catalyst or a silver complexing agent, e.g. Sodium thiosulfate.
  • a bleaching catalyst or a silver complexing agent e.g. Sodium thiosulfate.
  • the fixing bath can be composed in a known and customary manner.
  • the fixative used is e.g. Katrium thiosulfate or advantageously ammonium thiosulfate, if desired with additives such as sodium bisulfite and / or sodium metabisulfite.
  • the bathrooms have the following composition:
  • the cyan densities of the wedges obtained according to (A) are measured in the red spectral range using a reflectance densitometer.
  • the maximum cyan density is 2.5.
  • the silver densities are determined with the same instrument in the blue spectral range.
  • the cyan dye is bleached to a density of about 0.4 at the points with a silver density of 0.5.
  • the same amount of silver is used to bleach the cyan dye only to a density of about 0.9 [the color bleaching is inhibited by the compound of the formula (100)].
  • Example 3 Three further materials A, B and C are produced which are suitable for the production of positive overlay copies using the silver color bleaching process:
  • Material A is produced with an intermediate gelatin layer (Z1) which contains 4 g of gelatin per m 2 of substrate surface.
  • Material C shows no loss of dye in the magenta layer in spite of the equally thin intermediate layer (Z1) as in material B.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP84810036A 1983-01-26 1984-01-20 Matériel photographique pour le procédé de blanchiment des couleurs à l'argent Expired EP0117227B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH425/83 1983-01-26
CH425/83A CH656725A5 (de) 1983-01-26 1983-01-26 Photographisches material fuer silberfarbbleichverfahren.

Publications (3)

Publication Number Publication Date
EP0117227A2 true EP0117227A2 (fr) 1984-08-29
EP0117227A3 EP0117227A3 (en) 1985-08-21
EP0117227B1 EP0117227B1 (fr) 1988-03-23

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ID=4186731

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EP84810036A Expired EP0117227B1 (fr) 1983-01-26 1984-01-20 Matériel photographique pour le procédé de blanchiment des couleurs à l'argent

Country Status (5)

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US (1) US4576885A (fr)
EP (1) EP0117227B1 (fr)
JP (1) JPS59139030A (fr)
CH (1) CH656725A5 (fr)
DE (1) DE3470102D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0274357A3 (en) * 1987-01-06 1989-09-20 Ciba-Geigy Ag Process for treating exposed photographic silver dyebleaching materials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH466036A (fr) * 1965-08-19 1968-11-30 Kodak Sa Procédé de production d'une image en couleur et produit photographique pour la mise en oeuvre de ce procédé
US3457074A (en) * 1966-04-22 1969-07-22 Eastman Kodak Co Silver dye bleach element containing ballasted para-quinone as diffusion inhibitor
CH507536A (de) * 1968-04-09 1971-05-15 Ciba Geigy Ag Photographisches, Nitroverbindungen enthaltendes Material für das Silberfarbbleichverfahren
JPS5820424B2 (ja) * 1976-10-12 1983-04-22 富士写真フイルム株式会社 カラ−画像形成方法
JPS58203935A (ja) * 1982-05-05 1983-11-28 チバ・ガイギ−・アクチエンゲゼルシヤフト 新規な１，４−ベンゾキノン類

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0274357A3 (en) * 1987-01-06 1989-09-20 Ciba-Geigy Ag Process for treating exposed photographic silver dyebleaching materials

Also Published As

Publication number Publication date
EP0117227B1 (fr) 1988-03-23
CH656725A5 (de) 1986-07-15
JPS59139030A (ja) 1984-08-09
DE3470102D1 (en) 1988-04-28
EP0117227A3 (en) 1985-08-21
US4576885A (en) 1986-03-18

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