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
  • 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
• • 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

Definitions

• the invention relates to a photographic development process in which colored positive overlay images can be produced from either color negatives or color positives using only one color development bath.
• Colored supervisory images are essentially produced using two processes.
• One is the usual negative process, in which a color negative is exposed on a negative-working color paper, the color paper is developed with a color developer of the p-phenylenediamine series, the oxidation product of which reacts with the couplers in the material to produce desired dyes, then bleached and finally fixed, washed or is stabilized.
• the other is a reversal process in which a positive color image, for example from a color slide, is exposed onto a negative-working color paper, the color paper is developed imagewise with a black and white developer, then diffusely exposed or chemically fogged in order to develop completely undeveloped silver halide to make, and finally subjected to a color development, in turn, from the developer oxidation product of the color developer and the color couplers, the desired dyes. Bleaching, fixing, watering or stabilizing also follow here.
• the invention thus relates to a process for producing positive color images on a reflective base by exposing a color negative paper with either a color slide or a color negative, then in the first case black and white initial development, transfer to a color development bath, diffuse exposure and color development in the color development bath or in the second case direct introduction of the exposed material into the color development bath, bypassing the first development bath, both the first development bath and the color development bath containing a p-phenylenediamine compound as developer substance, the first development bath additionally containing a compound which prevents the coupling of the developer oxidation product with the color couplers of the material and the color development bath is designed so that the coupling of the developer oxidation product with the color couplers of the material is possible, the color paper contains silver bromide, silver chloride or silver chlorobromide emulsions, cyan couplers of the phenol type, magenta couplers of the 3-anilinopyrazolone or pyrazoloazole type and yellow couplers of the ⁇
• Coupling in the color development bath is made possible by increasing the pH and setting a lower concentration of coupling-preventing compound than in the first development bath.
• 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 ( CD 3), 4- (N-ethyl-N-2-hydroxyethyl) -2-methylphenylenediamine sulfate (CD 4) and 4-N, N-diethyl-2,2'-methanesulfonylaminoethylphenylenediamine hydrochloride.
• Suitable compounds which prevent the color couplers from reacting with the developer oxidation product are e.g. Citracic acid, sulfite, hydroxylamine and derivatives, ascorbic acid and derivatives and white couplers. They are preferably used in an amount of 0.005 to 0.1 mol / l.
• the coupling-preventing effect of these substances is eliminated in the color development bath, for example by setting a pH> 9.5.
• 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, hydroxyethyldiacetaminic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethylenediaminetic 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 e.g. 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 benzimidazoles and agents for adjusting the desired pH.
• the developer solutions can also contain less than 5 g / l of benzyl alcohol; they are 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 that 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 constantly results in one developer solution in use is added to that during development to replace used chemicals 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.
• Suitable for carrying out the method is a device with a plurality of treatment tanks to be passed through in succession, which are connected by transfer devices and at least one of which contains a color development bath and a further treatment tank is arranged in the direction of flow in front of this developer tank, which contains a first development bath that in addition to the Inlet opening in the tank of the first development bath a further inlet opening is provided at the end of a guide bridging the tank of the first development bath to the tank containing the color development bath, the tank containing the color development bath contains a lighting device for diffuse exposure of the material, which is switched on when in the tank material entering the color development bath had previously run into the tank containing the first development bath. The lighting device faces the layer side of the photographic material.
• the color negative paper 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, by reaction with alkylating or acylating agents or by Grafting of 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.
• gelatins The production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. 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.
• 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 suitable as silver halide emulsions.
• It can be predominantly compact crystals, which are, for example, regular cubic or octahedral or transitional forms can have.
• 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, for example 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 ⁇ m and 2.0 ⁇ m, the grain size distribution can be both 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.
• Suitable cyan couplers of the phenol type (BG), magenta couplers of the 3-anilinopyrazolone type (PP) and yellow couplers of the ⁇ -pivaloylacetanilide type (GB) are given below by way of example.
• Different color papers can be used for reverse processing on the one hand and negative processing on the other hand, for example with a flatter gradation for reverse processing and a steeper gradation for negative processing.
• This type of paper should have a medium gradation if possible.
• a color photographic recording material was produced by applying the following layers in the order given to a support on paper coated on both sides with polyethylene.
• the quantities given relate to 1 m2.
• the corresponding amounts of AgNO3 are given.
• a step wedge was exposed on the photographic material described above, and the material was passed in a device with a plurality of successive processing tanks connected by transfer means and at least one of which contained developer liquid suitable for developing copies of negative originals
• At least one further treatment tank was arranged in this developer tank for negative copies with a bath liquid causing a reversal development and, in addition to the inlet opening in the reversal development tank, a further inlet opening was provided at the end of a guide bridging the reversal development tank to the treatment tank suitable for the copies of negative originals , processed in such a way that the material was loaded directly into the development tank for copies of negative originals, bypassing the reverse development tank.
• Example 2 was repeated, but the negative development bath contained 10% by weight of the reverse development bath to simulate the steady state in which the reverse development bath is carried over from the reverse development tank to the negative development bath when changing from reverse to negative processing. (For the composition of the reverse development bath, see Example 5).
• the sensitometric data are given in the table below.
• a commercially available color reversal paper with emulsions based on AgBr (for the production of positive color copies of the slide after the reversal process) is processed in the intended process with the following processing baths:
• the processing baths had the following composition: Adjust the pH to pH 9.8 with KOH or H2SO4, make up to 1 liter with water. pH adjustment to pH 10.3 with KOH or H2SO4; Make up to 1 liter with water.
• the bleach-fix bath corresponded to Example 1.
• the procedure is as in Example 3, but the color developer contains 10% by weight of the first developer, while the color developer contains less Water is brought into the color development tank.
• the sensitometric data are given in the table below.
• a step wedge is exposed on the material of Example 1 and the material in the device of Example 1 is subjected to a reverse development, with the first development (reverse development) and a diffuse second exposure in the color development bath being added to Example 1.
• the reverse developer had the following composition:
• the reverse development time was 45s at 38 ° C.
• Example 5 was repeated with the color developer of Example 2.
• the sensitometric data can be found in the table below.
• Example 2 The procedure is as in Example 2, but the color developer is not mixed with the reverse developer according to the invention, but with the reverse developer according to the prior art (first developer from Example 3).
• the sensitometric data can be found in the table below.

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• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Citations (6)

• 1989
  • 1989-12-21 DE DE3942243A patent/DE3942243A1/de not_active Withdrawn
• 1990
  • 1990-12-08 DE DE59008933T patent/DE59008933D1/de not_active Expired - Fee Related
  • 1990-12-08 EP EP90123618A patent/EP0433812B1/fr not_active Expired - Lifetime
  • 1990-12-19 JP JP2411683A patent/JPH0418548A/ja active Pending

Patent Citations (6)

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