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
  • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings

Definitions

• the invention relates to an aqueous stabilizing bath and a method for stabilizing developed images with the aid of this stabilizing bath.
• Photographic images are usually subjected to washing after development and fixation are completed to improve stability. It is already known to replace irrigation with treatment in a so-called stabilizing bath.
• DE-A-3 123 771 specifies a water-free process with several stabilizing baths which contain a phosphonic acid and a fungicide and formaldehyde.
• DE-A 3 412 857 discloses stabilizing baths which contain metal ions, chelating agents and fungicides.
• a stabilizing bath which should serve as a replacement for the irrigation, must not be used promote due influence on the image dyes, no yellowing and no growth of microorganisms. In addition, they should be usable in the usual processing machines and enable perfect image production even when introducing components from upstream baths, in particular bleach-fix baths.
• the stabilizing bath remains clear when used. It is easy for microorganisms to spread and for silver sulfide to fail as a result of the decomposition of the introduced thiosulfate.
• the stabilizing baths known to date do not meet these requirements satisfactorily.
• the invention is based on the object of specifying an improved stabilizing bath which delivers very good results even under the heaviest loads in the practical field.
• the minimum densities should not deteriorate, the image dye densities should be retained, the growth of microorganisms should be suppressed and precipitation during use, e.g. of silver sulfide or sulfur should be avoided.
• Very particularly preferred chelating agents correspond to the following formula (III) wherein R 10 , R 11 and M have the meaning given under formula (II).
• Phosphonic acids to be used according to the invention are also understood to mean those which instead of a P0 3 M 2 group are a condensed phosphonic acid group, for example of the following structure exhibit.
• Preferred compounds of the formula (III) are given in the following table: It may K, the water-soluble sulfites are commonly used in photographic baths are used. Sulfites of the following cations are particularly preferred: ammonium, zinc, aluminum, alkali, in particular sodium or potassium and alkaline earth metal, in particular magnesium or calcium.
• esters of sulfurous acid are those of glycerol and pentaerythritol.
• a particularly preferred adduct is formaldehyde bisulfite.
• the pH of the stabilizing baths according to the invention is preferably between 0.5 and 10, in particular between 3.0 and 9.0 and very particularly preferably between 4.0 and 7.5.
• the stabilizing bath can be buffered in a manner known per se. Are particularly suitable for buffering Acetates, borates, metaborates, phosphates, monocarboxylates, dicarboxylates, polycarboxylates, oxycarboxylates, amino acid salts, aminocarboxylates, primary phosphates, secondary phosphates and tertiary phosphates.
• the treatment in the stabilizing bath takes place in the temperature range usually used, in particular between 20 and 45 ° C.
• the treatment time is preferably between 20 seconds and 5 minutes.
• the stabilizing bath according to the invention is carried out in the form of a cascade.
• Several stabilizing baths are used here.
• fresh stabilizing bath is preferably added to the last tank, so that it is the successive tanks against the direction of the processing photographic material.
• an excess of volume emerges from the first tank in the cascade.
• the inventive method comprises at least a developing step in which the exposed silver halide is reduced to silver in color photographic materials rafischen g bleaching for the oxidation of the reduced silver and a Fixage to remove the silver salts from the award materials.
• Bleaching and fixing can be combined in a manner known per se under certain circumstances.
• the usual conditions for color development can be observed during development.
• the development takes place at a pH of above 8, preferably above 9.5.
• the concentration of the color developer substances depends on the circumstances, a concentration of about 4 to 40 mmol / l of the ready-to-use developer solution is particularly preferred.
• the development can be in the presence of pH buffers, development inhibitors, antifoggants, water softening complexing agents, preservatives, CHANGES IN SBE accelerators, competitive couplers, fogging agents, Hill developer compounds and viscosity modifiers: see Research Disclosure 17 544 of December 1978, issued by Industrial Opportunities Ltd., Homewell Havant, Hampshire, UK, Section XXI and Ullmanns Encyclopedia of Industrial Chemistry, 4th Edition, Volume 18, 1979, particularly pages 451, 452 and 463 to 465. A detailed description of suitable developer compositions and processing methods is given by Grant Haist, Modern Photographic Processing, John Wiley and Sons, 1973, Volumes 1 and 2.
• the usual developer substances can be used in the context of the present invention. These preferably contain p-phenylenediamine derivatives as color developer substance, for example: N, N-dimethylp-phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline, 2-amino-5-diethylamino-toluene, N -Butyl-N- ⁇ -sulfobutyl-p-phenylenediamine, 2-amino-5- (N-ethyl-N- ⁇ -methanesulfonamidoethylamino) toluene, N-ethyl-N-ß-hydroxyethyl-p-phenylenediamine, N, N -Bis- (ß-hydroxyethyl) -p-phenylenediamine, 2-amino-5- (N-ethyl-NB-hydroxyethylamino) toluene.
• the developing bath contains the following developer substances A
• the developer bath can be supplemented in a known manner with a regeneration solution.
• Oxidation protection compounds such as e.g. Hydroxylamine, ascorbic acid, certain sugars and glusosamine, complexing agents, the usual buffer compounds, development accelerators, antifoggants, competitive couplers, surfactants and whiteners are added.
• Hydroxylamine ascorbic acid
• certain sugars and glusosamine complexing agents
• the usual buffer compounds development accelerators, antifoggants, competitive couplers, surfactants and whiteners
• the regeneration rate depends, among other things, on the composition of the recording material and the components of the regenerator solution.
• bleaching and fixing can be carried out in a conventional manner, and these steps can also be summarized.
• the usual bleaching agents can be used.
• Salts and complexes of trivalent iron and persulfates are particularly suitable.
• Suitable ferric complexes include complexes with aminopolycarboxylic acids such as ethylenediamine-tetraessi g- acid, nitrilotriacetic acid and 1,3-diamino-2-propanol tetraacetic acid and hexacyanoferrates.
• Conventional fixing baths containing a silver halide solvent as the main component can be used for the fixation.
• Thiosulfates are particularly preferred.
• the fixing baths can also contain sulfites, borates and other customary additives.
• the light-sensitive silver Halo enidemulsionsschtraum g of the materials to be processed preferably color couplers are assigned, which can react with the color developer oxidation products to form a dye.
• the color couplers are preferably directly adjacent to and in particular contained in the silver halide emulsion layer.
• the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or ⁇ -naphthol type.
• the green-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone type usually being used.
• the blue-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
• the color couplers can be, for example, 6, 4 and 2 equivalent couplers. Suitable couplers are known, for example, from the publications "Farbkuppler" by W.
• the usual mask couplers can be used to improve the color rendering.
• the recording material can also contain DIR compounds and white couplers which do not give any dye when reacted with color developer oxidation products.
• the inhibitors which can be split off from the DIR compounds can be split off directly or via non-inhibiting intermediate compounds.
• hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, especially gelatin. Casting aids and plasticizers can be used. Reference is made to the compounds indicated in Research Disclosure 17,643 above in Sections IX, XI and XII.
• the layers of the photographic material can be hardened in the usual manner, for example with hardeners of the epoxy type, the heterocyclic ethylene imine and the acryloyl type. Furthermore, it is also possible to harden the layers in accordance with the process of German laid-open specification 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible that the photographic layers or farbfolo g rafischen multilayer materials with hardeners of the diazine-triazine or 1,2-dihydroquinoline series to cure or hardeners of the vinylsulfone type. Further suitable hardening agents are known from German laid-open documents 2 439 551, 2 225 230, 2 317 672 and from Research Disclosure 17 643, section XI, specified above.
• a commercially available color paper with a blue, a green and a red-sensitive silver halide emulsion layer was exposed imagewise and processed as follows:
• step wedges processed in experiments a) to i) were subjected to storage at 60 ° C. and 90% relative humidity for a period of 7 days.
• Table Bl shows the changes in the yellow minimum density and the blue green density.
• the change in the blue green density is comparatively small, but there is an improved blue green resistance compared to the standard (test i).
• a standing test is carried out to show the influence of the bleach-fix bath substances introduced into a stabilizing bath on the condition and appearance of the solution, as well as the potential for microorganisms to act.
• the stabilizing baths according to experiment a-h of Example 1 are each divided into stages 1, 2 and 3 as described and left in open beakers at 20-25'C for 21 days.
• the evaporated volume is supplemented from time to time with distilled water.
• stage 1 Two different effects can occur during the service life.
• stage 2 Two different effects can occur during the service life.
• stage 3 a more or less dark precipitate can form from the introduced substances, which settles out or produces a cloudy solution.
• stage 3 molds can be seen on or in the solution and in stage 2 both effects can occur in a weakened form.
• Tables B1 and B2 show the advantageousness of the bath according to the invention according to test h: Favorable yellow minimum densities, blue green densities, no precipitation and no fungal growth are obtained.

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

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• 1985
  • 1985-06-25 DE DE19853522622 patent/DE3522622A1/de not_active Withdrawn
• 1986
  • 1986-06-12 EP EP86108036A patent/EP0206148B1/fr not_active Expired
  • 1986-06-12 DE DE8686108036T patent/DE3667342D1/de not_active Expired - Fee Related
  • 1986-06-25 JP JP61147242A patent/JPS623251A/ja active Pending

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