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
  • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
  • G03C7/421—Additives other than bleaching or fixing agents

Definitions

• the invention relates to bleaching baths for processing an exposed color photographic light-sensitive silver halide material in which the bleaching function is accelerated, as a result of which the processing time is shortened and also difficult to bleach image silver can be completely bleached.
• the minimum densities are reduced for reversible materials.
• the basic stages of processing color photosensitive materials generally include a color development stage and a silver removal stage. In the case of reversal materials, there is also an upstream black / white development and a second exposure. In the last stage, the silver produced during development is oxidized with a bleaching agent and dissolved with a fixing agent.
• the removal of the silver can be carried out in two stages with a bleaching bath and a fixing bath or in one stage with a bleach-fixing bath.
• the bleaching process is predominantly carried out using an iron (III) ion complex salt (for example aminopolycarboxylic acid iron (III) complex salt, in particular iron (III) ethylenediaminetetraacetate complex salt).
• iron (III) ion complex salt for example aminopolycarboxylic acid iron (III) complex salt, in particular iron (III) ethylenediaminetetraacetate complex salt.
• Iodoso compounds, persulfates, cobalt (III) ion complex salts and cerium IV ion complex salts are also suitable.
• iron (III) ion complex salts have a comparatively low oxidizing power. There has been a need, therefore, to increase the bleaching power of a bleaching solution or bleach-fixing solution containing a bleaching agent with a low bleaching power, in particular an iron (III) ion complex salt.
• bleach accelerators examples include thiourea derivatives (JP-OS 8506/70, US Pat. No. 3,706,561), selenourea derivatives (JP-OS 280/71), mercapto compounds with a five-membered ring (GB-PS 1 138 842), thiazole derivatives and thiadiazole derivatives ( CH-PS 336 257).
• 5-Mercaptotetrazole has also been used as an accelerating agent for the removal of silver in a bleaching Fixing solution used (GB-PS 1 138 842). However, these compounds have weak accelerating power, poor solubility, or poor stability in the processing solution.
• DE-OS 3 518 257 describes the bleaching accelerating effect of compounds of the formulas where R19 to R20 are hydrogen, alkyl, acyl or together the remaining members of a ring, m and l are an integer 1 to 3.
• bleach-fixing baths based on iron-III-EDTA are usually used after the first development, the second exposure and the color development to remove silver from the paper.
• bleach accelerators are added to the Bleach-fix bath required to effect bleaching sufficiently quickly and completely.
• compounds such as 3-mercapto-1,2,4-triazole or 5-amino-2-mercapto-1,3,4-triadiazole are used successfully.
• bleach accelerators in the bleach-fixer has also proven to be useful for color negative paper. If the bleaching is inadequate, residual amounts of silver remain in the materials, which in the case of the mostly IR-controlled cutting device can lead to incorrect information, by which the image strip is not cut between the images but in the middle of the images.
• bleach-fixing bath namely bleaching bath and fixing bath
• bleach accelerators cannot be used because they no longer have a sufficient, accelerating effect in the bleaching bath, and because some of them do not are sufficiently soluble or cause sediments.
• bleach accelerator Without bleach accelerator, the insufficiently bleached photo papers show considerable residual silver content in the dark areas of the image, which cannot be significantly reduced even by a longer bath time.
• the object of the present invention is to provide bleaching or bleach-fixing baths, preferably bleaching baths, which are stable and have an excellent bleaching rate and do not form any sediment. They are intended to ensure low minimum densities in the case of reversal materials during the usual processing times and to completely bleach the residual silver in the blacks in the case of color negative papers. Other photographic properties should not be deteriorated.
• bleaching or bleach-fixing baths which contain an iron (III) ion complex salt as bleaching agent are a 5- to 7-membered heterocyclic, at least one N- and at least one further heteroatom from the series O, N, S containing compound, which is substituted by -S ⁇ and carries a positive charge on a quaternary ring nitrogen atom, arranged in such a way that tautomeric charge balance to a neutral thione form is not possible.
• R2 is hydrogen, C1-C8-alkyl, C2-C8-alkenyl, heteroaryl, C5-C10-cycloalkyl and C6-C12-aryl, C1-C8-dialkylamino, optionally containing a hydrophilizing group
• R4 C1-C8-alkyl, heteroaryl, C5-C10-cycloalkyl and C6-C12-aryl, optionally containing a hydrophilizing group
• R5 is hydrogen, di-C1-C8-alkylamino, C1-C8-alkyl, C2-C8-alkenyl, heteroaryl, C5-C10-cycloalkyl and C6-C12-aryl, optionally containing a hydrophilizing group, mean, where R4 and R5 together can be the groups required to complete a heterocyclic ring; and Formula IV in the R6 C1-C8-alkyl, heteroaryl, C5-C10-cycloalkyl and C6-C12-aryl, optionally containing a hydrophilizing group, R7 is hydrogen, di-C1-C8-alkylamino, C1-C8-alkyl, C2-C8-alkenyl
• Sulfonamido stands for compounds of the general formula R15-SO2-NH-, where R15 is hydrogen, C1-C8-alkyl, C5-C7-cycloalkyl, C6-C12-aryl or heteroaryl.
• Sulfamoylamino stands for compounds of the general formula R16R17N-SO2-NH-, where R16 and R17 are the same or different and are hydrogen, C1-C8-alkyl, C5-C6-cycloalkyl, C6-C12-aryl or heteroaryl.
• Acylamino stands for compounds of the general formula R18-CO-NH-, where R18 is hydrogen, C1-C8-alkyl, C5-C7-cycloalkyl, C6-C12-aryl or heteroaryl.
• Heteroaryl in general represents a five- or six-membered optionally benzo-fused heteroaromatic ring containing 1 to 3 heteroatoms from the series N, O and S.
• Hydrophilizing group is understood to mean the following structures: COOH, SO3H, PO (OH) 2, CH2OH, - (O-CH2-CH2) 2 ⁇ 20-OH.
• Triazolium thiolates according to formula I are known from US 4,631,253 and the common preparation methods are described there.
• Examples of thiadiazolium thiolates according to formulas II and III and their representation are from Grashey, Baumann and Lubos, Tetrahedron Letters 1968, 5881 and Kier, Scott, J. Heterocycl. Chem. 5, 277, (1968).
• the oxadiazolium thiolates according to formulas IV are described by McCarthy, Ollis and Ramsden in J. Chem. Soc., Perkin Trans. I 1974, 627.
• Thiazolium thiolates of the formula V and imidozolium thiolates of the formula VI are published by Huisgen et al in THL 1967, 1809-14.
• the amount of the compound of the present invention in the bleaching and bleach-fixing baths varies depending on the kind of the processing solution, the kind of the photographic material to be processed, the processing temperature, the time required to perform the desired processing, etc. However, an amount is 1 x 10 ⁇ 5 to 1 mole per liter of bleaching or bleach-fixing bath is suitable, 1 x 10 ⁇ 3 to 1 x 10 Mol1 mol being preferred. In general, the best range is determined by simple preliminary tests.
• the compound to be used according to the invention can be added directly to the bleaching or bleach-fixing bath or introduced through an upstream conditioning bath.
• the bleaching baths according to the invention can also be used in rapid processing processes with development times of less than 60 seconds, the color photographic recording materials used there having chloride-rich silver halide emulsion layers (at least 80 mol% AgCl).
• Suitable iron (III) ion complex salts are complexes of iron (III) ions and a chelating agent such as an aminopolycarboxylic acid, an aminopolyphosphonic acid or a salt thereof, in particular an alkali metal salt or ammonium salt.
• Typical examples of chelating agents are ethylenediaminetetraacetic acid; Disodium ethylenediaminetetraacetate; Diammonium ethylenediaminetetraacetate; Tetra (trimethylammonium) ethylenediaminetetraacetate; Tetrapotassium ethylenediaminetetraacetate; Tetrasodium ethylenediaminetetraacetate; Trisodium ethylenediaminetetraacetate; Diethylenetriaminepentaacetic acid; Pentasodium diethylenetriaminepentaacetate; Ethylenediamine-N- ( ⁇ -hydroxyethyl) -N, N ′, N′-triacetic acid; Trisodium ethylenediamine-N- ( ⁇ -hydroxyethyl) -N, N ′, N′-triacetate; Triammonium ethylenediamine-N- ( ⁇ -hydroxyethyl) -N, N ′, N′-triacetate; Propyl
• the iron (III) ion complex salt can be used in the form of the complex salt or prepared in situ in the bleach or bleach-fix bath. Suitable cations are alkali cations and ammonium; the latter is preferred.
• the bleaching solution of the present invention may contain rehalogenating agents such as bromides (e.g. potassium bromide, sodium bromide, ammonium bromide, etc.), chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride, etc.) and the like in addition to the bleaching agents.
• rehalogenating agents such as bromides (e.g. potassium bromide, sodium bromide, ammonium bromide, etc.), chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride, etc.) and the like in addition to the bleaching agents.
• additives which have a pH buffering action such as inorganic acids, organic acids or the salts thereof, which are known for use in conventional bleaching solutions (for example boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid , Phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid,
• the pH of the bleaching solution is preferably 3.0 to 8.0, in particular 4.0 to 7.0.
• conventional fixing agents ie water-soluble, silver halide dissolving agents, such as thiosulfate (eg sodium thiosulfate, ammonium thiosulfate, ammonium sodium thiosulfate, potassium thiosulfate, etc.); Thiocyanates (eg sodium thiocyanate; Ammonium thiocyanate; Potassium thiocyanate, etc.); Thioether compounds (e.g. ethylene bisthioglycolic acid, 3,6-dithia-1,8-octanediol, etc.); and thioureas can be used alone or in a combination of two or more.
• special bleach-fixing agents containing a combination of a fixing agent and a large amount of a halide compound such as potassium iodide can also be used.
• the ferric ion complex salt is usually present in an amount of 0.1 to 1 mol / l.
• the amount of the fixing agent is generally 0.2 to 4 mol per liter of the bleach-fixing solution.
• Bleach-fix solutions can also contain preservatives such as sulfites (e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.), hydroxylamine, hydrazine, aldehyde-bisulfite adducts (e.g. acetaldehyde sodium bisulfite adduct), etc.
• sulfites e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.
• hydroxylamine e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.
• hydroxylamine e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.
• hydroxylamine e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.
• hydroxylamine e.
• the pH of the bleach-fix solution when used is usually 4.0 to 9.0, particularly preferably 5.0 to 8.0.
• a color negative paper with a silver chloride bromide emulsion (80% AgBr and 20% AgCl) is exposed behind a step wedge and processed as follows: Color developer 210 sec. 33 ° C Watering 20 sec. 20 ° C Wiping the water off the surface of the pictures Bleach bath 50 sec. 20 ° C Watering 60 sec. 20 ° C Fixer 60 sec. 20 ° C Watering 120 sec. 20 ° C dry
• the step wedges shown are examined with a PM 8030 infrared silver detector from Photo-Matic, Denmark.
• the table below shows whether residual silver is still present in the blackening after using the freshly prepared bleaching bath.
• the resistance of the bleaching bath was tested after 4 and 15 days of standing at 33 ° C.
• sediment formation was assessed after 15 days of inactivity, which can occur especially when a bleach bath containing silver ions is in use.
• Example 1 is repeated, 2.2 g of thioglycerol / l being added to the bleaching bath as the reference substance.

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

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• 1987
  • 1987-12-23 DE DE19873743783 patent/DE3743783A1/de not_active Withdrawn
• 1988
  • 1988-12-09 US US07/282,121 patent/US4939075A/en not_active Expired - Fee Related
  • 1988-12-14 EP EP88120873A patent/EP0321839B1/fr not_active Expired - Lifetime
  • 1988-12-14 DE DE8888120873T patent/DE3875930D1/de not_active Expired - Fee Related
  • 1988-12-20 JP JP63319684A patent/JPH01201659A/ja active Pending

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