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
• • 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
  • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof

Definitions

• the present invention relates to a color developer, as well a kit and a method for producing such Color developer according to the preambles of claims 1, 11 and 15.
• Color developers have become photographic in the prior art Development of color negative films, reversal films and color papers (Negative and reverse paper) is used.
• the real one Developer chemical is a reducing agent.
• the Color developers therefore usually contain preservatives in the form of antioxidants to prevent unwanted premature Oxidation of the developer chemical during storage or to prevent the application (e.g. by atmospheric oxygen) or at least to delay.
• sulfites and hydroxylamine are known as antioxidants (Ullmann's Encyclopedia of Industrial Chemistry, 5. Edition A20. P. 62).
• antioxidants Ullmann's Encyclopedia of Industrial Chemistry, 5. Edition A20. P. 62
• various hydroxylamine derivatives to use as a preservative.
• These derivatives are typically made by reacting Hydroxylamine with a second compound, such as, for example, chloroethanesulfonate, produced.
• a hydroxylamine derivative is formed, disulfoethylhydroxylamine (DSEHA) in the example mentioned.
• DSEHA disulfoethylhydroxylamine
• the hydroxylamine can either be a leaving group substitute the second compound (as mentioned above Example) or to an olefinic double bond second connection can be added.
• the reaction product is then cleaned (for example by recrystallization) and in Pure form of the developer solution added (EP-A-0 415 455, p. 11).
• Color developers are also known (EP-A-0 589 624, EP-A-0 682 289, EP-A-0 687 951). You will especially then used when it is on small transport volume and / or clean Handling arrives, furthermore they can be refreshed of development solutions in continuously working development machines be used.
• the addition of hydroxylamine derivative in a purified form as a preservative Granulated developers are also known (EP-A-0 682 289).
• the present invention has for its object a To create color developers of the type mentioned, whose Manufacturing requires less effort.
• the invention also relates to a kit for production a color developer in which at least one component this kit contains a hydroxylamine derivative described above Form of the reaction solution of the starting substances used for the preparation has been added.
• the color developer or its components can become one Solid with a moisture content of 0.5 - 5%, preferably 1.5 - 3%.
• the invention is based on the surprising finding that it is not necessary to have the preservative in the form to use a hydroxylamine derivative in purified form.
• the effect and quality of the color developer will not or only slightly affected if the reaction mixture instead the starting substances used for the production is used.
• This is all the more surprising since, for example. in the substitution reaction described above as an example HCl as a principle photographically active substance in the reaction solution remains, their dissolved substances constituent of the developer.
• Also used in the reaction to manufacture of the hydroxylamine derivative is often not hydroxylamine in pure form, but in the form of a salt (e.g. a hydrochloride or sulfate salt) used. In no case results however, there is a noticeable deterioration in quality and function of the developer.
• color developer denotes in the context of the invention any mixture of substances used to develop color negative and reversal films, as well as color negative and reversal papers can be used.
• the hydroxylamine derivative is in the form of the reaction solution used for the production of starting substances. This means that the reaction mixture does not have a separate purification step subjected to isolation of the hydroxylamine derivative color developer as a preservative is added immediately.
• the reaction for producing the hydroxylamine derivative can for example an addition reaction, a substitution reaction or include a Mannich-type reaction. Provided it is a reaction in the course of which a halide (Chloride) is released, this halide can simultaneously as an antifoggant in the color developer Act. The quantity of the is then advantageously separated added antifoggants such as sodium or potassium chloride reduced accordingly.
• a halide Chloride
• L preferably denotes a straight chain or a branched alkylene group with 1 to 10, preferably 1 to 5 carbon atoms.
• Preferred examples of the ingredient -L-A of formula (I) include the carboxymethyl, carboxyethyl and Carboxypropyl group, the sulfoethyl, sulfopropyl and sulfobutyl group, furthermore the phosphonomethyl, phosphonoethyl and the hydroxyethyl group.
• the term amino, ammonium and Carbamoyl radical in the claims includes both corresponding unsubstituted as well as substituted residues.
• Residues are substituted, they are preferably with an alkyl group which is branched or unbranched can be, and preferably 1 to 10, more preferably Contains 1 to 5 carbon atoms.
• the hydroxylamine derivative is preferably selected from the group consisting of Disulfoethylhydroxylamine, N-hydroxyiminodiacetic acid, N-hydroxyiminodipropionic acid, N-hydroxyiminodimethylenephosphonic acid, and salts of the aforementioned substances.
• the color developer according to the invention can be formulated as a solid be. In this case, it is preferably in the form granules, pellets or tablets pressed granules.
• the different procedures for Granulation or pellet formation are familiar to the person skilled in the art and include, for example, granulation in drums, by extrusion, compression, Breaking, stirring, and by fluidized bed processes and by spray drying. Since in the context of the invention as Preservative-added hydroxylamine derivative in the form a reaction solution, it is particularly preferred spray this reaction solution into a fluidized bed granulator, in which the remaining components of the to be manufactured Color developer or the corresponding component of the Kits are located and at the desired final moisture content to dry.
• the reaction solution of the hydroxylamine derivative not subjected to any preparation before use must be, the preparation is formulated as a solid Color developer significantly simplified.
• the moisture content of a solid formulation according to the invention Color developer is preferably between 0.5 and 5%, more preferably between 1.5 and 3%. A color developer with these moisture levels shows during storage no significant in the absence of air and at room temperature Discoloration, clumping or change in breaking strength.
• the color developer according to the invention can present as granules.
• the grain size of the granulate is preferably 50-1000 ⁇ m, more preferably 150 - 500 ⁇ m. Alternatively, it can be in pellet or tablet form (the granulate is preferably compressed into tablets) available.
• the color developer according to the invention can be used as a multi-component kit usually with 2 or 3 components (e.g. solutions or granules) are sold, which the user before the Use to a finished color developer solution.
• the color developer in the form of all the necessary ingredients Solid (preferably granules, pellets or tablets) to bring the market.
• This solid can be particularly easily prepared for a finished color developer solution or to refresh an existing developer solution be used.
• the color developer in the form of a so-called mono concentrate, d. H. as a finished, concentrated color developer solution to bring to the market.
• the components of this Mono concentrate may be not completely in the aqueous Solvent soluble, so that the concentrate as a solid-liquid mixture is present. The invention has recognized that this the usability of a color developer prepared from the concentrate not affected.
• a color developer according to the invention is in one step hydroxylamine or its salt with a Compound containing the residue -L-A or a precursor thereof for the preparation of a hydroxylamine derivative of the formula (I) reacted.
• a preliminary stage of -L-A is everyone Substance that with the hydroxylamine and possibly another Substance such as formaldehyde to a hydroxylamine derivative of Formula (I) reacts.
• this precursor contain a vinyl component.
• the reaction solution comes with without further refurbishment or cleaning the other components of the color developer or the corresponding Combined component of a kit.
• reaction solution is preferably sprayed on.
• the excess Water is removed by drying, so that a Solid with the desired moisture content arises.
• the hydroxylamine is in here Form of the hydrochloride used so that sodium chloride as A by-product of the reaction is formed.
• reaction volume contains of 166 ml (assuming 100% yield) 66 g (0.25 mol) of the final product and 14.6 g (0.25 mol) NaCl.
• a color developer of the prior art which contains the following components per liter of working solution: CD-3 5.0 g optical brightener Tinopal SFP® 1.5 g KCl 3.5 g K 2 CO 3 27.0 g DTPA (diethylenetriaminepentaacetic acid) 3.0 g DSEHA (disulfoethylhydroxylamine) from Iwako, Japan 9.5 g
• This developer becomes a photographic developer of a Kodak RA-4 control strip used in the RA-4 color paper process.
• the one with this developer of the prior art developed control strip serves as a reference for the densitometric measurements described below.
• Chloride compensation means that the KCl content of the developer solution is reduced to the extent that by adding the reaction solution chloride in the form of NaCl in the Developer solution is introduced. In experiments VI and VII it is ensured that the chloride content is compared does not change the reference developers of the prior art.
• 1000 g potassium carbonate, 10 g sodium sulfite, 100 g DTPA-5Na (Diethylenetriaminepentaacetic acid pentasodium salt), 50 g tinopal SFP® and 100 g lithium hydroxide monohydrate are mixed on one Grain size ⁇ 150 ⁇ m milled.
• the mixture is 250 g mannitol and 150 ml of water are added and it is 10 min at room temperature granulated. Then the granules at 60 ° C. dried in a fluid bed dryer to a residual moisture of 2%.
• Granules B1 (comparison, not according to the invention)
• 500 g CD-3 are ground to a grain size ⁇ 200 microns and mixed with 50 g sorbitol.
• the mixture is placed in a fluidized bed granulator given and at 40 ° C within 4 740 ml of the reaction solution from Example 1 were sprayed in.
• the concentration of the hydroxylamine derivative in this reaction solution is (assuming 100% yield) 405 g DSEHA-2Na per liter. It is obtained after the spraying has been completed one dried to a residual moisture of less than 2% Granules.
• the granules A and B2 together form a kit for production a color developer according to the invention.
• Color developer tablets such as are made from these granules manufactured as follows:
• 1000 g potassium carbonate, 12 g sodium sulfite, 100 g DTPA-5Na, 45 g sodium toluenesulfonate and 100 lithium hydroxide monohydrate are ground to a grain size of ⁇ 150 microns and with 250 g Sorbitol mixed.
• the mixture is added with the addition of 145 ml Water granulated at room temperature for 15 minutes and then at 60 ° C in a fluid bed dryer to a residual moisture dried by 2%.
• 600 g of sodium toluenesulfonate and 300 g of DSEHA-2Na are on a grain size of ⁇ 150 microns ground. Then follows Granulation with the addition of 170 ml of water. In a fluid bed dryer is at 50 ° C to a residual moisture of dried below 2%. In this comparative example the preservative hydroxylamine derivative in Pure form has been added.
• 500 g of sodium toluenesulfonate have a grain size of about Ground 200 ⁇ m and mixed with 150 g sorbitol.
• the mixture is placed in a fluidized bed granulator and 620 ml of the reaction solution from Example 5 are in a Temperature of 40 ° C sprayed over a period of 5 min.
• the concentration of this reaction solution of N-hydroxyiminopropionic acid disodium salt is at a theoretical Yield of 100% of the reaction from Example 5 360 g per liter. After granulating and drying you get a granulate with a residual moisture below 2%.
• the granules A, B and C1 (comparative example) as well as A, B and C2 (example according to the invention) are in each case in the to the so-called Final mixes mixed. These final mixes can be immediate as color developers, but they will preferably compressed into tablets.
• the two final granulate mixtures according to the invention from Examples 7 and 8 and the two comparison granules (Mixtures A, B2, as well as A, B, C2 on the one hand and A, B1, as well A, B, C1 on the other hand) and those pressed from these final mixtures Tablets are stored in the absence of air for 6 weeks. Neither storage at room temperature for this period even at 50 ° C cause significant changes in the With regard to clumping or influencing the breaking strength. A slight brown color has no influence the photographic result.
• the bleach-fix bath is adjusted to a pH of 6.2.
• the temperature of the baths is 35 ° C.
• the developers and bleach-fix baths used become Development of a Kodak RA-4 control strip in the RA-4 color paper process used. Color development and bleach fixation are carried out for 45 s each.
• Densitometric measurements of fog, sensitivity, contrast and final density d max are carried out on the developed control strips. All measured values in the inventive as well as in the comparative examples lie within the tolerance limits specified by Kodak for the RA-4 color paper process.

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Citations (6)

• 1997
  • 1997-12-22 EP EP97122660A patent/EP0851289A3/fr not_active Withdrawn

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