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
  • G03C7/28—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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/40—Chemically transforming developed images
  • G03C5/44—Bleaching; Bleach-fixing

Definitions

• the present invention relates to a new process for processing exposed and developed silver color bleaching materials and preparations suitable for this process in form. of ready-to-use aqueous solutions or of water-dilutable concentrates in liquid or solid form.
• the preparations used for the color and / or silver bleaching or the combined bleach fixation: (baths) are strongly acidic. i.e. have a pH of less than 2. especially under 1. This pH is generally set using strong acids, primarily mineral acids, such as hydrochloric acid, sulfuric acid, nitric or phosphoric acid, and also sulfamic acid. Even with certain strong organic acids. such as p-toluenesulfonic acid, good results are obtained.
• Hydrochloric acid highly volatile and therefore has a particularly corrosive effect on e.g. Apparatus and devices in which the processing of the photographic material is carried out.
• the sulfamic acid which is suitable per se and can easily be produced in free-flowing powder form, can in many cases be used as a substitute for liquid mineral acids.
• One disadvantage is their relatively poor solubility in water. It has also been shown that it reacts with tertiary phosphines, which are used as bleach accelerators, and leads to unstable bleaching baths.
• p-Toluenesulfonic acid which can also be used in free-flowing powder form, has a high water solubility and provides stable bleaching baths.
• the object of the present invention is to provide strong mineral acids, as are required in the processing of photographic silver color bleaching materials, in a suitable form in order to overcome the disadvantages mentioned above.
• the present invention relates to a process for processing exposed and developed photographic silver color bleaching materials by treating the exposed and developed material with aqueous bleaching preparations which contain (a) an acid component, (b) a silver complexing agent, (c) one or more bleaching catalysts, ( d) optionally an antioxidant, (e) optionally a water-soluble oxidizing agent and (f) optionally a bleach accelerator, characterized in that component (a) is a water-soluble adduct of an acid amide or a lactam and a strong mineral acid.
• the invention further relates to the preparations for carrying out the process, the concentrates or partial concentrates for the preparation of the ready-to-use aqueous preparations and the use of the adducts of acid amides or lactams and strong mineral acids in aqueous preparations for silver and / or color bleaching, and also a Process for the preparation of urea-sulfuric acid adducts.
• the acid amides used to prepare the adducts with the strong mineral acids are those of low molecular weight aliphatic acids, for example with 1 to 4, in particular 1 or. 2, carbon atoms, also of monocyclic aromatic acids, such as in particular benzoic acids optionally substituted with alkyl (C 1 -C 4 ), halogen, nitro or cyano, and also the diamides (ureas) of carbonic and thiocarbonic acids.
• the nitrogen atoms of the amides can be substituted with alkyl having 1 to 4 carbon atoms, in particular with methyl, or in particular disubstituted.
• suitable amides are thiourea, benzamide and preferably urea, formamide, dimethylformamide, acetamide and dimethylacetamide.
• Suitable lactams are those of y, ⁇ - and ⁇ -amino acids (4 to 6 carbon atoms), which may be substituted on the nitrogen atom with lower alkyl (C 1 -C 4 ), in particular with methyl.
• Examples of the lactams mentioned are piperidone ( ⁇ -valerolactam) and in particular.
• Strong mineral acids include phosphoric acid and perchloric acid, and in particular sulfuric acid, hydrochloric acid or other hydrohalic acids (HBr, HJ) and nitric acid.
• Table 1 shows the composition of the properties of various mineral acid adducts of amides and lactams.
• the generally colorless and stable addition compounds are partly liquid and partly occur in crystallized form. As far as possible, the melting points of crystalline products are given.
• the connections are partly hygroscopic.
• the mineral acid adducts of urea are particularly well known, in particular the adducts of one mole of urea with 0.5 or 1 mole of sulfuric acid.
• Information about the properties of these adducts, their stability, the reaction kinetics in the melt and in aqueous solutions can be found, among others. at L.H. Dalman, J.Am.Chem.Soc. 56, 549 (1934) P. Baumgarten, Chem. Ber. 69, 1929 (1936), E. Cherbuliez & F. Landolt, Helv. 29, 1438 (1946) and G.M. Schwab & E. Schwab-Agallidis, Angew. Chemie, 65, 418 (1953).
• the mineral acid adducts of urea are produced either directly from the components or their solutions or else by the action of mineral acids on cyanamide, the latter becoming. Urea decomposes, which then enters into the addition compound with the acid.
• Harastoff mineral acid adducts can be found, inter alia, in German patent specification 239 309, American patent specification 3 330 864 or in English patent specifications 196 601 and 1 109 619.
• the adducts used according to the invention can be stored in solid molded goods and can easily be produced in the form of free-flowing water-soluble powders or granules.
• the melt can be removed by suitable methods, e.g. used in the production of alkali metal hydroxides (cf. Ullmanns Encyklopadie der Technische Chemie, 4th edition, Verlag Chemie, Weinheim, Vol. 17 (1979), p. 204 f), are converted into a solid form suitable for the application. In particular, it can be crystallized in the form of free-flowing pearls, pills, flakes or flakes that are immediately soluble in water.
• the sulfuric acid adducts can be brought into the form of beads if they are e.g. sprayed in a cooling tower.
• the sulfuric acid adducts of urea can also be prepared in an aqueous medium. Thereafter, urea is introduced into an aqueous sulfuric acid solution at about 50 ° C. with stirring. A suspension of the crystallizing urea sulfate is thus obtained, which is filtered off and optionally dried (cf. Ullmanns Encyklopadie der Technische Chemie, 4th edition, Verlag Chemie, Weinheim, 2, 154, 672, 698 (1972)).
• solid, hygroscopic acids can also be brought into a less hygroscopic form.
• trichloroacetic acid and p-toluenesulfonic acid completely dissolve when exposed to an atmosphere with 76X relative humidity.
• the adducts of these acids with e.g. However, urea, pyrrolidone or thiourea remain in crystalline form under the conditions mentioned.
• the most important constituents of the baths used for color bleaching are a strong acid in the form of the acid adduct (a), a complexing agent for the silver (b) and a color bleaching catalyst (c).
• Diazine compounds such as pyrazine, quinoxaline or phenazine and their derivatives are primarily used as color bleaching catalysts.
• Suitable bleaching catalysts are e.g. known from German patents and patent publications Nos. 735 672, 1 547 720, 2 144 297, 2 144 298, 2 722 776 or 2 722 777.
• a suitable silver complexing agent can e.g. Be thiourea.
• a water-soluble iodide alkali metal iodide, preferably sodium or potassium iodide, furthermore ammonium iodide
• an antioxidant must be used to prevent the iodide from oxidizing to iodine.
• Reductones or water-soluble mercapto compounds are advantageously used as antioxidants (d).
• Examples include the particularly preferred formaldebydisulfite adduct, and also the corresponding adducts of acetaldehyde, propionaldehyde, butyraldehyde or isobutyraldehyde, of glyoxal, malondialdehyde or glutardialdehyde.
• the tertiary water-soluble phosphines mentioned below as bleach accelerators can also be used simultaneously as antioxidants.
• oxidizing agent Water-soluble aromatic mononitro and dinitro compounds and anthraquinone sulfonic acid derivatives are expediently used as the oxidizing agent (s).
• the use of such oxidizing agents also serves to influence the color balance and the contrast of the images produced by the color bleaching process and is known from German patent specification 735,672, British patent specifications 539 190 and 539 509 and Japanese patent publication 22673/69.
• the compounds of component (e) serve to flatten the gradation.
• Suitable bleach accelerators (f) are e.g. quaternary ammonium salts as are known from German Offenlegungsschriften 2 139 401 and 2 716 135. It is preferred. quaternary, optionally substituted piperidine, piperazine, pyrazine,
• tetraalkylammonium compounds (alkyl with 1 to 4 carbon atoms) and alkylenediammonium compounds (alkylene with 2 to 6: carbon atoms) come into question.
• N-hydroxyethyl pyridinium chloride N-hydroxypropyl pyridinium bromide; N-methyl-2-hydrogymethylpyridinium iodide; N, N-dimethylpiperidinium iodide ;. N, N'-dimethylpyrazinium fluorosulfate and y-picolinium bisulfate.
• Further bleaching accelerators are the water-soluble tertiary phosphines known from DE-OS 2 651 969, which preferably contain at least one cyanoethyl group.
• X is optionally substituted alkyl and Y is hydroxyalkyl, alkoxyalkyl, sulfoalkyl, aminoalkyl (alkyl of 1 to 25, preferably 2 to 4 carbon atoms), phenyl, sulfophenyl or pyridyl.
• Preferred tertiary phosphines correspond to the formula wherein X 1 -CH 2 CH 2 CN or - (CH 2 ) 2 OCH 3 , Y 1 - (CH 2 ) 2 SO 3 ⁇ M ⁇ , - (CH 2 ) 3 -SO 3 -M ⁇ , - (CH 2 ) 4 -SO 3 ⁇ M ⁇ , - (CH 2 ) 2 OCH 3 or -CH 2 N (C 2 H 5 ) 2 , W 1 -CH 2 CH 2 CN or phenyl and M ⁇ a cation, in particular an alkali metal cation, eg the sodium or potassium cation.
• a cation in particular an alkali metal cation, eg the sodium or potassium cation.
• Baths of conventional composition can be used for silver development, e.g. those which contain hydroquinone as developer and optionally additionally 1-phenyl-3-pyrazolidinone.
• the silver development bath may already contain a bleaching catalyst.
• the silver fixing bath can be composed in a known and customary manner.
• the fixative used is e.g. Sodium thiosulfate or advantageously ammonium thiosulfate, optionally with additives such as sodium bisulfite and / or sodium metabisulfite.
• the fixing bath can also be combined with the bleaching bath as a so-called bleach-fixing bath.
• the temperature of the bleaching baths is generally between 20 and 90 ° C., preferably between 20 and 64 ° C., the processing time required being of course shorter at a higher temperature than at a lower temperature.
• the bleaching baths are stable within the specified temperature range.
• the aqueous bleaching preparations required for processing are used in the form of dilute aqueous solutions which contain the components mentioned.
• other methods are also conceivable, e.g. application in paste form.
• the aqueous bleaching preparation according to the present invention can be produced, for example, from solid or liquid, in particular aqueous concentrates of individual or all components ((a) to (f)). It is advantageous to use, for example, a solid and a liquid or two liquid concentrates, one of which contains the acid adduct (a) and the oxidizing agent (e) and the other of which contains the other components (b), (c) and optionally (d) and (f) , in the latter concentrate to improve the solubility., in particular component (c), an additional solvent such as ethyl or propyl alcohol, ethylene glycol methyl or ethyl ether can be added.
• These concentrates (partial concentrates), which are also the subject of the present invention, have excellent stability and can therefore be stored for a long time. These concentrates can, if necessary, be used after dilution with water or with a mixture of water and an organic solvent.
• the concentrates of the individual or all components (a) to (c) and optionally (d) to. (f) or their combinations, for example from component (a) and (e) and from components (b), (d), (c) and ( f ), can be 2 to 20 times, preferably 5 to Contain 10 times the amount of the individual components per liter of concentrated preparation, as previously stated for the ready-to-use bleach baths. They are usually available as solid, liquid or pasty concentrates.
• the present invention further relates to the process for processing exposed and developed silver color bleaching materials, characterized in that it is carried out using aqueous bleaching preparations which contain components (a) to (c) and, if appropriate, (d) to (f) becomes.
• aqueous bleaching preparations which contain components (a) to (c) and, if appropriate, (d) to (f) becomes.
• These bleaching preparations can be color or silver bleach baths, combined color and silver bleach baths or bleach-fix baths.
• the method according to the invention can e.g. in the production of positive color images in automatic copying or recording machines or in the rapid processing of other silver color bleaching materials such as for scientific records and industrial purposes, e.g. colored screen photography, are also used for the production of color negatives and diffusion transfer images.
• a transparent, metallic-reflective, or preferably white-opaque material which is unable to absorb liquid from the baths, can be used as a support for photographic materials to be processed.
• the carrier can for example consist of optionally pigmented cellulose triacetate or polyester. If it consists of paper felt, it must be coated on both sides or with. Polyethylene coated.
• the photosensitive layers are located on at least one side of this support, preferably in the known arrangement, i.e. a red-sensitized silver halide emulsion layer containing a blue-green azo dye on the bottom, a green-sensitized silver halide emulsion layer containing a purple azo dye above and a blue-sensitive silver halide emulsion layer containing a yellow azo dye above.
• the material can also contain sub-layers, intermediate layers, filter layers and protective layers, but the total thickness of the layers is usually intended. Do not exceed 20 ⁇ .
• the method according to the invention is also particularly suitable for processing exposed silver color bleaching material which has a special structure and e.g. is suitable for producing self-masked images (DE-OS 2 547 720).
• Example 1 A material suitable for the production of positive overlay copies of a positive original for the silver color bleaching process was produced in the following way:
• This material is constructed in such a way that, when processed with a developer containing a silver ligand, in particular sodium thiosulfate, and the subsequent process steps of color and silver bleaching necessary for the silver color bleaching process, the latter preferably combined in a single step, and finally the fixation, a masking of the blue secondary color densities the magenta and Blaugrü n layer is effected.
• a sample strip is cut from this photographic material and exposed additively behind a gray wedge as follows:
• Example 2 The photographic material used in Examples 2 and 3 below is identical to that of Example 1, with the exception of filter layer (6), which this time contains only colloidal silver but no additional unsensitized emulsion.
• the processing sequence is similar to that of Example 1, but the silver developing solution does not contain sodium thiosulfate, which does not produce a self-masking effect.
• a sample strip of the photographic material was exposed additively, similar to that described in Example 1, using the following exposure times:
• the processing temperature was 30 ° C throughout the processing.
• a second test strip is exposed in the same way and treated in the same processing solutions, but using a bleaching bath containing 17 ml / liter of 96% sulfuric acid.
• the finished treated and dried test strips give identical sensitometric values, with a D max of each
• Example 3 The 9-layer unmasked material used in Example 2 is additively exposed behind a gray wedge in the same way as there and then subjected to a processing sequence with four baths, in which a separate bath is used for the successive color and silver bleaching.
• a second sample strip is exposed and processed in an identical manner, however. 14 ml of 96% sulfuric acid in the color bleaching solution and 20 ml of 96% sulfuric acid in the silver bleaching solution are used per liter of solution.
• the two positive gray wedges obtained in this way corresponded in all sensitometric values.
• the measured maximum and minimum densities (reflectance densities) are:
• Example 4 In this example, using the same dyes as in Example 1, a six-layer material is used which in the first layer contains the blue-green dye and the associated red-sensitized silver halide emulsion, and the second layer contains a thin, pure gelatin-containing intermediate layer in the third layer contains the purple dye with the associated green-sensitized silver halide emulsion, the fourth layer contains an intermediate layer consisting of gelatin, the fifth layer contains a silver halide layer containing a yellow dye and finally the sixth layer contains a protective layer made of pure gelatin.
• a so-called two-bath process consisting of a developer bath and a subsequent combined bath, in which the dye and silver bleaching and the fixing take place practically simultaneously.
• An identical bath as in Example 3 is used as the silver developing bath; the combined bleaching and fixing bath has the following composition:
• a second sample strip is exposed and processed in an identical manner, but using a combined bleaching and fixing bath which contains 9.5 g / l of 96% sulfuric acid.
• the finished and dried test strips each result in a positive gray wedge. identical sensitometric values.
• the measured densities reflectance values.
• Example 5 Concentrate for the preparation of a combined color and silver bleach bath.
• a preparation consisting of a solid and a liquid partial concentrate is prepared as follows:
• a combined color and silver bleach bath is prepared by dissolving part III and part IV in 900 g of water.

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1981
  • 1981-02-17 US US06/235,388 patent/US4366232A/en not_active Expired - Fee Related
  • 1981-02-17 DE DE8181101124T patent/DE3170675D1/de not_active Expired
  • 1981-02-17 EP EP84108556A patent/EP0131970B1/fr not_active Expired
  • 1981-02-17 EP EP81101124A patent/EP0034793B1/fr not_active Expired
  • 1981-02-21 JP JP2369881A patent/JPS56132340A/ja active Granted
• 1988
  • 1988-09-12 US US07/244,632 patent/US4879413A/en not_active Expired - Fee Related

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