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

Definitions

• the invention relates to an improved reverse process with chemical fogging, chemical fogging baths and their use for the production of photographic images.
• the imagewise exposed photographic material is first developed with a first developer. After that, exposure is uniform and the material thus exposed is subjected to the second development with a black and white or color developer. The process is completed by bleaching and / or fixing or bleaching the photographic material.
• the veiling baths known from German Offenlegungsschriften 1,814,834 and 2,009,693 contain complexed tin-II ions as veiling agents. Although the concentration of oxidizable free metal ions in these baths is kept extremely low, the oxidizability is still present to such an extent that further stabilization of the fogging agents against atmospheric oxygen is necessary. Furthermore, such reducing processing baths show a pronounced tendency to form mold with longer service lives.
• the stability of the obscurants increases with the falling pH of the solutions containing them.
• a general use of strongly acidic solutions of the fogging agents is opposed, however, by the fact that the dyes customary in photographic materials are attacked in part in the more acidic range and that, in the case of a desirable direct transition of the photographic material from the bath containing the fogging agent, acids in the alkaline color developer not exactly controllable dimensions are introduced into the color developer and can impair the color developer activity.
• radicals R 1 , R 2 , R 3 , R 4 and R 5 can optionally be substituted even with photographically acceptable radicals.
• substituents are in particular alkyl, in particular with max. 4-C atoms; Cycloalkyl, preferably with 5 or 6 carbon atoms; Aryl, especially phenyl and heterocyclyl.
• Acyl radicals are understood in particular to be those which are derived from aliphatic or aromatic carboxylic or sulfonic acids, including carbonic acid monoesters, carbamic acids or sulfamic acids.
• Examples of such acyl radicals are formyl, acetyl, benzoyl, phenylcarbamoyl, ethoxycarbonyl.
• Suitable stabilizers are, for example, acetyl-2-phenylhydrazine and hydroxylammonium sulfate.
• 5- or 6-membered N-containing radicals are particularly preferred as heterocyclic radicals.
• Suitable amounts of stabilizing agents are between 0.5 mmol and 200 mmol, preferably between 2 mmol and 20 mmol per liter of the corresponding bath.
• the amount of stabilizing agent is measured in such a way that sufficient stabilization of the fogging agent is guaranteed, but on the other hand is so small that the stabilizing agent itself only acts to a minor extent on the photographic material.
• the pH of the baths to be used according to the invention can be varied within wide limits and is preferably between pH 3 and pH 8. Excellent results are obtained in particular at these pH values if the presence of a suitable buffer in the bath provides sufficient buffer capacity in the desired pH Area is guaranteed.
• the fogging agents can be used in the usual concentrations.
• To regenerate the V Veil baths can also use liquid concentrates of high concentration, which can be diluted up to 100 times.
• the stabilizers to be used according to the invention can be prepared by known processes, such as described in Houben-Weyl, volume 10/4, page 192 ff. and in Chemischeberichte, 101 (1968), page 3344 ff.
• a particularly suitable phosphonocarboxylic acid is 1,2,4-tricarboxybutane-2-phosphonic acid.
• the complexing agents mentioned can be used in the baths to be used according to the invention individually or in combination and, if appropriate, in excess, based on the tin (II) ions present.
• the method according to the invention is applicable to the treatment of a light-sensitive, photographic material, which contains couplers.
• couplers These compounds can be the usual color couplers, which are usually incorporated into the silver halide densities themselves.
• the red-sensitive layer contains 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 contains at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or indazolone type usually being used.
• the blue-sensitive layer unit contains at least one non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
• Color couplers of these types are known in large numbers and are described in a large number of patents. Examples include the publication "Color coupler” by W. PELZ in “Messages from the research laboratories of Agfa, Leverkusen / Kunststoff", Volume III (1961) and K. VENKATARAMAN in "The Chemistry of Synthetie Dyes", Vol. 4, 341 - 387, Academio Press, 1971.
• 2-equivalent couplers can be used as non-diffusing color couplers; these contain a removable substituent in the coupling point, so that they only require two equivalents of silver halide to form the color, in contrast to the usual 4-equivalent couplers.
• the 2-equivalent couplers that can be used include, for example, the known DIR couplers, in which the cleavable residue acts as a diffusing development inhibitor after reaction with color developer oxidation products is set free.
• the so-called white couplers can also be used to improve the properties of the photographic material.
• the non-diffusing color couplers and coloring compounds are added to the light-sensitive silver halide emulsions or other casting solutions by customary known methods. If the compounds are soluble in water or alkali, they can be added to the emulsions in the form of aqueous solutions, if necessary with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide, as far as the non-diffusing color couplers and coloring agents are concerned.
• Compounds are water- or alkali-insoluble compounds, they can be emulsified in a known manner, for example by mixing a solution of these compounds in a low-boiling organic solvent directly with the silver halide emulsion or first with an aqueous gelatin solution, after which the organic solvent is removed in a conventional manner.
• a gelatin emulsate of the respective compound thus obtained is then mixed with the silver halide emulsion.
• coupler solvents or oil formers are additionally used to emulsify such hydrophobic compounds; these are generally higher-boiling organic compounds, which include the compounds in the form of oily droplets which split off the non-diffusing color coupler and development inhibitor to be emulsified in the silver halide emulsions.
• coupler solvents or oil formers are additionally used to emulsify such hydrophobic compounds; these are generally higher-boiling organic compounds, which include the compounds in the form of oily droplets which split off the non-diffusing color coupler and development inhibitor to be emulsified in the silver halide emulsions.
• the customary silver halide emulsions are suitable for the present invention. These can contain silver chloride, silver bromide, silver iodide or mixtures thereof as silver halide.
• Gelatin is preferably used as a
• binders e.g. Alginic acid and its derivatives such as salts, esters or amides, cellulose derivatives such as carboxymethyl cellulose, alkyl cellulose such as hydroxyethyl cellulose, starch or their derivatives such as ethers or esters or caragenates are suitable.
• Synthetic binders include polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and the like.
• the emulsions can also be chemically sensitized, e.g. by adding sulfur-containing compounds during chemical ripening, for example allyl isothiocyanate, allyl thiourea, sodium thiosulfate and the like.
• Reducing agents e.g. the tin compounds described in Belgian patents 493 464 or 568 687, also polyamines such as diethylenetriamine, or aminomethanesulfinic acid derivatives, e.g. B. according to Belgian patent 547 323 used.
• Precious metals such as gold, platinum, palladium, iridium, ruthenium or rhodium and compounds of these metals are also suitable as chemical sensitizers.
• the emulsions can also be spectrally sensitized, for example by the customary mono- or polymethine dyes, such as acidic or basic cyanines, hemicyanines, streptocyanines, merocyanines, oxonols, hemioxonols, styryl dyes or other, also tri- or polynuclear methine dyes, for example rhodacyanines or neocyanines.
• the customary mono- or polymethine dyes such as acidic or basic cyanines, hemicyanines, streptocyanines, merocyanines, oxonols, hemioxonols, styryl dyes or other, also tri- or polynuclear methine dyes, for example rhodacyanines or neocyanines.
• sensitizers are described, for example in the work of FM HAMER "The C Yanine Dyes and Related Com
• the emulsions can contain the usual stabilizers, such as, for example, homeopolar or salt-like compounds of mercury with aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
• stabilizers are also suitable as stabilizers.
• azaindenes preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such compounds are described in the article by BIRR, Z.Wiss.Phot., 47, 2-58 (1952).
• Other suitable stabilizers include heterocyclic mercapto compounds, for example phenyl mercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.
• the emulsions can be hardened in the usual manner, for example with formaldehyde or halogen-substituted aldehydes which contain a carboxyl group such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes and the like.
• the photographic layers can be hardened with hardeners of the epoxy type, the heterocyclic ethylene imine or the acryloyl type.
• hardeners of the epoxy type, the heterocyclic ethylene imine or the acryloyl type. Examples of such hardeners are described, for example, in German Offenlegungsschrift 2,263,602 or British Patent 1,266,655.
• hardeners examples include alkyl or arylsulfonyl group-containing diazine derivatives, derivatives of hydrogenated diazines or triazines, such as 1,3,5-hexahydrotriazine, fluorine-substituted diazine derivatives, such as fluoropyrimidines, esters of 2-substituted 1,2-dihydroquinoline or 1,2-dihydroisoquinoline-N-carboxylic acids.
• vinyl sulfonic acid hardeners carbodiimide or carbamoyl hardeners, as described, for example, in German Offenlegungsschriften 2 263 602, 2 225 230 and 1 808 685, French Patent 1 491 807, German Patent 872 153 and GDR Patent 7218.
• Other useful hardeners are described, for example, in British Patent 1,268,550.
• Suitable are e.g. Films made from cellulose nitrate, cellulose acetate, such as cellulose triacetate, polystyrene, polyester, such as polyethylene terephthalate, polyolefins, such as polyethylene or polypropylene, a barytized or a polyolefin-laminated, e.g. a polyethylene-coated paper base, as well as glass and the like.
• photographic reversal material is exposed imagewise with at least one silver halide emulsion layer and subjected to a black-and-white development and, if necessary, a stop bath and watering.
• the photographic material is then treated in a bath with the solution of the fogging agents stabilized according to the invention. If necessary, this bath, which contains the fogging agents, can be combined with a bath which is customary between the first and second development of the photographic material.
• the photographic material thus treated is developed in a second developer to form a positive reverse image.
• the usual reagents can be used to adjust an alkaline pH in the second developer.
• the second developer can also contain the usual components, such as complexing agents.
• the photographic material may after the treatment with the bath containing the fogging agent, but far before the development Z, are treated with an alkaline bath.
• the advantage of the method according to the invention compared to the previously used concealment methods lies in the stabilization of the concealment agents, which is ensured in particular also at higher pH values between pH 3 and pH 8.
• This stabilizing effect, in particular that of hydroxylamine is all the more astonishing, since it is known, for example, that hydroxylamine can have an oxidizing effect on tin-II compounds and thus the use of hydroxylamine as an antioxidant for veiling baths is contrary to considerable prejudices.
• the well-known strong tendency to mold growth can be effectively suppressed.
• a commercially available reversible multilayer color photographic material with a red-sensitive, a green-sensitive and a blue-sensitive silver halide emulsion layer containing color couplers for the respective partial images in the corresponding light-sensitive layers is exposed imagewise in a conventional manner.
• the exposed color photographic material is then subjected to an initial development in a developer of the following composition (quantity per liter):
• the photographic material treated in this way is subjected to a stop bath and a wash and bleached and fixed in a known manner and subjected to a final wash.
• the tin-II complex of ethylenediaminetetraacetic acid is prepared in accordance with the information in German Offenlegungsschrift 1 814 834, Example 7, page 23. 3.0 g of stannous chloride hydrate and the amounts of residual reactants corresponding to this amount are used. The resulting solution of the tin-II complex is mixed with so much water that three samples (samples A, B and C) of 900 ml are obtained upon division.
• Sample A is adjusted to pH 5 and made up to 1000 ml with water.
• Sample B is mixed with 3.0 g of acetyl-2-phenylhydrazine, dissolved in 20 ml of methanol.
• the pH is adjusted to 5 with sodium acetate and the solution is made up to 1000 ml with water.
• Sample C is mixed with 2.7 g of hydroxylammonium sulfate.
• the pH is adjusted to 5 with sodium acetate and the solution is made up to 1000 ml with water.
• Example 1 The reversed multilayer color photographic material described in Example 1 is exposed and processed as described in Example 1, with the modification that the prebaths listed below are used instead of the prebaths described in Example 1.
• the tin-II complex of gluconic acid is prepared as described in British Patent 1,467,007, page 2, lines 50-65.
• the solution obtained is diluted with water in such a way that its content of stannous ions per liter corresponds to that of the preliminary baths.
• the same volume as the pre-baths D, E and F is used as the pre-bath.
• Example 1 The reversed multilayer color photographic material described in Example 1 is exposed and processed as described in Example 1, only the prebaths H, I and K described below are used instead of the prebaths described in Example 1.
• prebaths H, I and K To prepare these prebaths, 6.5 g of the disodium salt of 1-hydroxyethane-1,1-diphosphonic acid are dissolved in 50 ml of water and mixed with 5 g of stannous chloride hydrate. This solution is mixed with sodium hydroxide solution until a clear solution is obtained. The pH of this solution is adjusted to 5 and the solution is then made up to 100 ml with water. 10 ml of this solution are used to prepare the preliminary baths H, I and K.
• 10 ml of the solution are diluted to 800 ml with water and buffered by adding glacial acetic acid and sodium acetate. The pH is adjusted to 5 and the solution is finally made up to 1000 ml with water.
• Example 1 The reversed multilayer color photographic material described in Example 1 is exposed and processed as described in Example 1, only the pre-baths L and M described below are used instead of the prebaths described in Example 1.
• prebaths L and M 5 g
• stannous chloride 5 g
• a 50% solution of 1,2,4-tricarboxybutane-2-phosphonic acid 5 g
• This solution is made up to 100 ml with water. 10 ml of this solution are used to prepare the preliminary baths.
• 10 ml of the solution are made up to 1000 ml with water and the pH is adjusted to pH 5 with NaOH.
• hydroxylammonium sulfate 2.7 g are dissolved in 950 ml of water and mixed with 10 ml of the above solution.
• the pH is adjusted to pH 5 with NaOH and the volume is made up to 1000 ml with water.
• prebath M The freshly prepared baths L and M guarantee an excellent maximum color density. After a standing time of 8 days, however, there is a clear drop in the color densities obtained with prebath L, while excellent maximum color densities are still obtained when using the process according to the invention (prebath M), as can be seen from Table 4 below.
• Example 1 The reversed multilayer color photographic material described in Example 1 is exposed and processed as described in Example 1, only the pre-baths N, O, P and Q described below are used instead of the pre-baths described in Example 1.
• pre-baths N, O, P and Q are used instead of the pre-baths described in Example 1.
• To prepare these prebaths 36 g of trisodium citrate x 5.5H 2 0 are dissolved in 150 ml of water and, after addition of 10 g of stannous chloride dihydrate, stirred until a clear solution is obtained. The pH is adjusted to 5.0 with citric acid or NaOH, then made up to 200 ml with water.

Landscapes

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

Applications Claiming Priority (2)

Publications (2)

Family

ID=6020488

Family Applications (1)

Country Status (5)

Cited By (2)

Families Citing this family (3)

Citations (10)

Family Cites Families (5)

• 1977
  • 1977-10-01 DE DE19772744356 patent/DE2744356A1/de not_active Withdrawn
• 1978
  • 1978-09-19 DE DE7878100932T patent/DE2860782D1/de not_active Expired
  • 1978-09-19 EP EP78100932A patent/EP0001415B1/fr not_active Expired
  • 1978-09-29 CA CA000312402A patent/CA1146791A/fr not_active Expired
  • 1978-09-30 JP JP11992278A patent/JPS5458439A/ja active Pending
• 1979
  • 1979-10-22 US US06/087,050 patent/US4299913A/en not_active Expired - Lifetime

Patent Citations (10)

Also Published As

Similar Documents

Legal Events