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
  • G03C7/407—Development processes or agents therefor
  • G03C7/413—Developers
  • G03C7/4136—Developers p-Phenylenediamine or derivatives thereof
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/305—Additives other than developers
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/50—Reversal development; Contact processes

Definitions

• the invention relates to a method for processing photographic reversal materials, which is of considerably shorter duration than conventional methods.
• a positive colored image is formed using a color slide by exposing a negative working color reversal paper through a special reversal development.
• the color reversal paper has at least one blue-sensitive silver-sensitive layer containing a yellow coupler, at least one green-sensitive layer containing green-sensitive and at least one red-sensitive silver halide layer containing a cyan coupler.
• the silver halide which was exposed imagewise during the exposure, is developed by a first developer into a black and white negative.
• Metol-hydroquinone or phenidone-hydroquinone developers are generally used.
• - Intermediate washing removal of the first developer to avoid post-development in the color development bath.
• - Diffuse second exposure or chemical fogging Everything silver halide not developed in the first developer is made developable.
• Color development development of the silver halide activated by the second exposure or chemical fogging into silver and dye formation.
• the dyes are formed in a corresponding amount from the color coupler and the developer oxidation product formed.
• - Bleaching and fixing or bleach-fixing removing all of the silver formed in the initial and color development, so that a positive dye image remains.
• - Final washing or stabilizing bath washing out chemicals and stabilizing image dyes and image surface.
• Postponement of the first developer would, however, be of minor importance if it were comparable to the structure of the color developer and would not cause any side reactions in the color development bath.
• DE-A-2 249 857 describes a process for reverse development in which both a black-and-white developer and a color developer who is disabled in his color coupling activities are used in the first development bath is set. In a second bath, the coupling-inhibiting effects caused, for example, by sulfite, ascorbic acid, etc., are eliminated and the color coupling can take place.
• the disadvantage of this process is the simultaneous presence of two types of developer and the resulting coordination and process problems. Overall, only a moderate image quality is achieved.
• the object of the invention was now to develop a reversal development method in which washing between the first and color development baths and diffuse second exposure can be dispensed with without the disadvantages mentioned above occurring.
• the present invention relates to a photographic reversal process for producing positive photographic images by imagewise exposure of the light-sensitive material containing at least one silver halide emulsion layer, initial black and white development of the material, chemical fogging, color development, bleaching, fixing, washing or stabilizing and drying, in which the material is transferred from the first development to the color development without any intermediate steps such as intermediate washing or diffuse second exposure, the first development bath contains only one or more N, N-dialkyl-p-phenylenediamine derivatives as developers and at least one tin (II) complex compound and to a pH Value is set to ⁇ 8, and the color development bath likewise exclusively contains one or more N, N-dialkyl-p-phenylenediamine derivatives as developer and is set to a pH value> 10.
• Suitable developer substances of the p-phenylenediamine type correspond to the general formula wherein R1, R2 H, optionally substituted C1-C4 alkyl, C6-C10 aryl and C1-C3 alkoxy, R3 H, optionally substituted C1-C4-alkyl, C6-C10-aryl and C1-C3-alkoxy, halogen, n is 1 or 2.
• Particularly suitable primary aromatic amino developer substances are p-phenylenediamines and in particular N, N-dialkyl-p-phenylenediamines, in which the alkyl groups and the aromatic nucleus are substituted or unsubstituted.
• N, N-diethyl-p-phenylenediamine hydrochloride 4-N, N-diethyl-2-methylphenylenediamine hydrochloride, 4- (N-ethyl-N-2-methanesulfonylaminoethyl) -2-methylphenylenediamine sesquisulfate monohydrate, 4- (N-ethyl-N-2-hydroxyethyl) -2-methylphenylenediamine sulfate and 4-N, N-diethyl-2,2'-methanesulfonylaminoethylphenylenediamine hydrochloride.
• the concentrations of the developer substances in the first development bath are in the range from 2 to 20 g / l, preferably 4 to 10 g / l.
• no developer substances are added to the second development bath, so that only the portions introduced from the first development bath are contained.
• the first development bath preferably contains at least one substance which prevents the color coupler from reacting with the developer oxidation product.
• Suitable compounds are e.g. Citracic acid, sulfite, hydroxylamine and derivatives, ascorbic acid and derivatives and colorless couplers that lead to colorless coupling products (white couplers). They are preferably used in an amount of 0.005 to 0.1 mol / l.
• the concentration of the tin (II) complex compounds in the first development bath is 0.001 to 0.05 mol / l.
• carboxylic acids and phosphonic acids are particularly suitable, such as. B .:
• Aminocarboxylic acids such as. B. ethylenediaminetetraacetic acid and those mentioned in German Offenlegungsschrift 1 814 834; Hydroxy carboxylic acids such as gluconic acid and citric acid; Polycarboxylic acids such as oxalic acid; Phosphonic acids of the type of nitrilomethylenephosphonic acids and alkylidenephosphonic acids, as described, for example, in the German patent application 2,009,693 are listed, azacycloalkane-2,2-diphosphonic acids as known from German Offenlegungsschrift 2,610,678 or phosphonocarboxylic acids with at least one carboxy and at least one phosphono group in the molecule, in particular acids of the following general formula: wherein R4, R5, R6, R7 are the same or different and are hydrogen, alkyl having 1 to 4 carbon atoms, hydroxyl or (CH2) m X, where X can be a phosphono or a carboxy group and m
• a particularly suitable phosphonocarboxylic acid is 1,2,4-tricarboxybutane-2-phosphonic acid.
• the complexing agents mentioned can be used in the baths to be used according to the invention individually or in combination and, if appropriate, in excess, based on the tin-II ions present.
• the first developer contains a phosphate or acetate buffer and is adjusted to a pH ⁇ 7.
• compounds which are intended to prevent a reaction of the developer oxidation product with the color coupler can be dispensed with.
• wetting agents and complexing agents to the two developer solutions, which accelerate the penetration of the solutions into the emulsion layers or bind calcium ions from the gelatin and the water.
• Suitable complexing agents for complexing calcium ions are, for example, aminopolycarboxylic acids, which are well known per se.
• aminopolycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid (EDTA), 1,3-diamino-2-hydroxypropyltetraacetic acid, diethylenetriaminepentaacetic acid, N, N'-bis- (2-hydroxybenzyl) -ethylenediamine-N, N'-diesiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid,
• calcium complexing agents are polyphosphates, phosphonic acids, aminopolyphosphonic acids and hydrolyzed polymaleic anhydride, e.g. Sodium hexametaphosphate, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotrismethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid.
• 1-hydroxyethane-1,1-diphosphonic acid also acts as an iron complexing agent.
• Special iron complexing agents are, for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 5,6-dihydroxy-1,2,4-benzenetrisulfonic acid and 3,4,5-trihydroxybenzoic acid.
• the iron complexing agent is used in amounts of about 0.02 to about 0.2 moles per mole of developer substance.
• Optical brighteners e.g. Polyalkylene glycols, surfactants, stabilizers, e.g. heterocyclic mercapto compounds or nitrobenzimidazole and means for adjusting the desired pH.
• the developer solution may also contain less than 5 g / l benzyl alcohol; it is preferably free of benzyl alcohol.
• the ready-to-use solutions can be prepared from the individual components or from so-called concentrates, the individual components being dissolved in the concentrates in a much higher concentration.
• the concentrates are adjusted so that a so-called regenerator can be produced from them, i.e. a solution which has somewhat higher concentrations of the individual components than the ready-to-use solution, on the one hand results in a ready-to-use solution by further dilution and addition of a starter and on the other hand always gives one developer solution in use is added to replace the chemicals consumed during development or chemicals carried over from the developer solution by overflow or by the developed material.
• the photographic material is bleached, fixed, washed and dried as usual, bleaching and fixing can be combined for bleach-fixing, and the washing can be replaced by a stabilizing bath.
• Color reversal photographic paper is particularly suitable as color reversal material, which is in particular a paper laminated with a barite layer or preferably an ⁇ -olefin polymer layer (e.g. polyethylene) onto which the light-sensitive layers are applied.
• a barite layer or preferably an ⁇ -olefin polymer layer (e.g. polyethylene) onto which the light-sensitive layers are applied.
• ⁇ -olefin polymer layer e.g. polyethylene
• the material usually contains at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer as well as, if necessary, intermediate layers and protective layers.
• Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.
• Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers.
• Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers.
• Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, Cellulose, sugar, starch or alginates.
• Semi-synthetic gelatin substitutes are usually modified natural products.
• Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose as well as gelatin derivatives which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers are examples of this.
• the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
• functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
• the gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used. The preparation of such gelatins is described, for example, in The Science and Technology of Gelatine, edited by AG Ward and A. Courts, Academic Press 1977, page 295 ff.
• the gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
• the silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide.
• the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide.
• Silver bromide chloride emulsions with on the one hand at least 80 mol% bromide and 0 to 20 mol% chloride and on the other hand with at least 95 mol% chloride and 0 to 5 mol% bromide are preferred. It can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms.
• platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
• the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, e.g. 12: 1 to 30: 1.
• the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as doping of the individual grain areas, being different.
• the average grain size of the emulsions is preferably between 0.2 .mu.m and 2.0 .mu.m, the grain size distribution can both be homo- and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%.
• the emulsions can also contain organic silver salts, for example silver benzotriazolate or silver behenate.
• Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
• the photographic emulsions can be spectrally sensitized using methine dyes or other dyes.
• Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
• Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromides.
• the differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it.
• cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.
• Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type.
• Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type.
• Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the ⁇ -acylacetamide type; Suitable examples are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers.
• a color photographic recording material which is suitable for the processing method according to the invention was produced by applying the following layers in the order given to a layer support on paper coated on both sides with polyethylene.
• the quantities given relate to 1 m2.
• the corresponding amounts of AgNO3 are given.
• green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.6 ⁇ m) from 0.45 g AgNO3 with 1.08 g gelatin 0.41 g purple coupler M 0.08 g 2,5-dioctyl hydroquinone 0.5 g DBP 0.04 g CPM
• Red-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 ⁇ m) from 0.3 g AgNO3 with 0.75 g gelatin 0.36 g cyan coupler C 0.36 g CPM
• a step wedge is exposed on the photographic material described above and processed as follows: First developer 45 sec, 30 ° C Color developer 45 sec, 30 ° C Bleach-fix 45 sec, 30 ° C Soak (3 x 15 sec) 45 sec, 30 ° C dry
• the individual processing baths had the following composition: First developer water 800 ml 4- (N-ethyl-N-2-hydroxyethyl) -2-methylphenylenediamine sulfate monohydrate (CD 4) 7 g Sn (II) phosphonobutane tricarboxylic acid 3.2 g Sodium sulfite 0.6 g Citracin acid 5 g Potassium carbonate 20 g pH adjustment to 7.5, then fill up to 1 liter with water.
• Citracin acid 5 g Potassium carbonate 20 g pH adjustment to 7.5, then fill up to 1 liter with water.
• Bleach-fix bath water 800 ml EDTA 4 g Ammonium thiosulfate 100 g Sodium sulfite 15 g Ammonium iron EDTA complex 60 g 3-mercapto-1,2,4-triazole 2 g pH adjustment to pH 7.3 with ammonia or acetic acid; Make up to 1 liter with water.
• First developer water 800 ml CD 3 10 g Sodium sulfite 10 g KH2PO4 20 g Sn (II) ions (as a complex compound) 0.3-3 g pH adjustment to 5.5 to 7.5; Make up to 1 liter with water Second developer water 900 ml KH2PO4 30 g CD 3 0-5 g Sodium sulfite 0-5 g Sn (II) ions (as a complex compound) 0-1 g pH adjustment to 10-13 with KOH; Make up to 1 liter with water.
• ethylenediaminetetraacetic acid oxalic acid or gluconic acid are suitable as complexing agents.
• the second developer can also contain conventional development accelerators such as ethylenediamine or thioether.

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• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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• 1989
  • 1989-11-11 EP EP89120978A patent/EP0370348A1/de not_active Withdrawn
  • 1989-11-13 US US07/434,414 patent/US5006439A/en not_active Expired - Fee Related
  • 1989-11-20 JP JP1299898A patent/JPH02184846A/ja active Pending

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