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
  • G03C7/392—Additives
  • G03C7/39296—Combination of additives
• • 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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/39212—Carbocyclic
  • G03C7/39216—Carbocyclic with OH groups
• • 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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/3924—Heterocyclic
  • G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
  • G03C7/39248—Heterocyclic the nucleus containing only nitrogen as hetero atoms one nitrogen atom

Definitions

• the invention relates to a color photographic recording material having at least one light-sensitive silver halide emulsion layer and at least one purple color coupler assigned to this layer.
• the invention further relates to a method for producing color photographic images.
• the ratio of gelatin to other compounds in this layer can become very high, so that additional gelatin often has to be used.
• the layers become thicker and less sharp.
• the object of the invention is to improve the light stability of images obtained from magenta color couplers, in particular of the pyrazolone type.
• a color photographic recording material with at least one light-sensitive silver halide emulsion layer and at least one magenta color coupler assigned to this layer has now been found.
• at least one layer S which does not contain a purple color coupler contains at least one diffusion-resistant indole derivative and at least one diffusion-resistant hydroquinone derivative.
• Layer S is preferably adjacent to a layer containing a purple coupler.
• the green-sensitive layer is preferably separated from the blue-sensitive and red-sensitive layers by a layer S.
• the indole derivative corresponds to the following formula I. in what mean R1 H, halogen, alkyl, aryl, amino, NHSO2X, NH-COX, NH-SO2NR5R6, NH-CONR5R6, X organic residue, especially a non-colored residue, R2 H, alkyl, aryl, - COOR5, R3 H, alkyl, aryl, acyl, -SO2-alkyl, -SO2-aryl, R4 H, halogen, nitro, alkyl, alkoxy, -NH-SO2-alkyl, -NH-SO2-aryl, -NH-CO-alkyl, -NH-CO-aryl, -S-alkyl, -S-aryl, -SO2-alkyl, SO2-aryl, R5 H, alkyl, aryl R6 H, alkyl, aryl, n is 0 or an integer from 1 to 4, with the proviso
• radicals R 1 are H, -NH-SO2-alkyl, -NH-SO2-aryl, -NH-CO-alkyl, -NH-CO-aryl, wherein R5 and R6 have the meaning given above.
• R1 is hydrogen or -NH-SO2-X
• X is an optionally substituted alkyl radical with preferably 1 to 20 C atoms
• an optionally substituted aryl radical for example phenyl or naphthyl or an optionally substituted heterocycle, preferably a 5 to 6-membered nitrogen-containing heterocycle.
• the hydroquinone derivative corresponds to the following formula II in what mean R10, R12: identical or different, namely hydrogen, alkyl, in particular with 1 to 18 carbon atoms, COR14, R15-COOR16 or SO3H
• R11 is hydrogen, alkyl, in particular with 4 to 20 C atoms or R15COOR16
• R13 is hydrogen or alkyl with 1-8 C atoms
• the hydroquinone derivative corresponds to the following formula III in what mean R20 alkyl with 1 to 10 carbon atoms or CO-R26 R21 H or R20 R22-R25 identical or different, hydrogen or alkyl having 1 to 20 carbon atoms, the sum of the carbon atoms preferably being between 8 and 40.
• One of the substituents is preferably hydrogen.
• the hydroquinone derivative corresponds to the following formula IV in what mean R30 R36-COOR37
• R31 is hydrogen or R30 R32-R35 the same or different, hydrogen or alkyl having 1 to 18 carbon atoms, the sum of the carbon atoms preferably being between 8 and 40, and preferably one of the ligands is hydrogen R36 polymethylene with 3 to 20 carbon atoms R37 (poly) methylene with 1 to 8 carbon atoms.
• indole derivatives are given below:
• Other suitable indole compounds correspond to the following formula wherein R has the following meaning Further suitable indole compounds are given in Research Disclosure 18226 (April 1980) No. 1 to 15.
• Suitable hydroquinone derivatives are the following compounds
• the hydroquinone derivatives and indole derivatives are each preferably used in an amount of 30 to 150 mg / m 2, in particular 50 to 100 mg / m2. Since the compounds are sparingly soluble in water, they can be treated in a manner known per se with an oil former, e.g. Tricresyl phosphate emulsified and then added to the casting solution.
• an oil former e.g. Tricresyl phosphate emulsified
• the indole and hydroquinone derivatives can be emulsified together or separately.
• the indole and hydroquinone derivatives can optionally be combined with other photographic building blocks, e.g. UV absorbers are emulsified and added.
• the stability of the dyes formed from magenta color couplers is improved by the combination according to the invention without having to accept the disadvantages to be feared. If indole derivatives without hydroquinone derivatives are added to interlayers, they hardly have any effect. If the indole compounds are added to the silver halide emulsion layer containing magenta couplers, the light stability of the magenta dye is even significantly deteriorated. The whites also change color strongly.
• the color photographic recording materials each contain at least one silver halide emulsion layer unit for recording light from each of the three spectral ranges red, green and blue.
• Each of the mentioned silver halide emulsion layer units can comprise a single silver halide emulsion layer or also a plurality of silver halide emulsion layers.
• Color photographic recording materials with double layers for the different spectral ranges are known, for example, from US Pat. Nos. 3,663,228, 3,849,138 and 4,184,876.
• Color photographic recording materials with triple layers are known from DT-OS 2 018 341 and DE 3 413 800.
• a blue, a green and a red-sensitive silver halide emulsion layer are contained in the order given on a layer support.
• the green-sensitive layer is separated from the adjacent light-sensitive layers by at least one layer S to be used according to the invention.
• the layer S to be used according to the invention does not contain any light-sensitive silver halide.
• layer S preferably contains at least one UV light-absorbing compound.
• formalin scavengers e.g. the iminopyrazolones known from DE-A-3 148 108 and US-A-4 414 309 can be contained.
• non-light-sensitive auxiliary layers can be present in the color photographic recording material according to the invention, which contain indole and hydroquinone derivatives, for example adhesive layers, antihalation layers or outer layers, in particular intermediate layers between the light-sensitive layers, which causes the diffusion of developer oxidation products from one layer to another should be effectively prevented.
• intermediate layers can also contain certain compounds which are able to react with developer oxidation products, for example scavengers, DIR couplers and also DAR couplers.
• Such layers are preferably sandwiched between adjacent photosensitive layers different spectral sensitivity arranged.
• a less sensitive silver halide emulsion with an average grain diameter of about 0.1 ⁇ m or smaller, which contains chloride, bromide and optionally iodide, can also be embedded in intermediate layers. Such a layer has a particularly beneficial effect on the sensitivity of the adjacent layers.
• the less sensitive silver halide emulsion can, however, also be introduced directly into the light-sensitive layers.
• Color couplers which can react with color developer oxidation products to form a dye, are preferably assigned to the light-sensitive silver halide emulsion layers.
• 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 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 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 color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
• the color couplers can e.g. are 6, 4 or 2 equivalent couplers.
• Suitable couplers are known, for example, from the publications "Color Coupler” by W. Pelz in “Messages from the Research Laboratories of Agfa, Leverkusen / Kunststoff", Volume III, page 111 (1961), K. Venkataraman in “The Chemistry of Synthetic Dyes", Vol. 4, 341 to 387, Academic Press (1971) and TH James, "The Theory of the Photographic Process", 4th Ed., Pp. 353-362, and from Research Disclosure No. 17643 of December 1978, Section VII, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, PO9 1 EF in the UK.
• the usual mask couplers can be used to improve the color rendering.
• the recording material can also contain DIR compounds and other 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.
• Suitable mask couplers are given below:
• Suitable DIR couplers have the following structure, for example:
• the light-sensitive silver halide emulsions used can contain chloride, bromide and iodide or mixtures thereof as the halide.
• the halide content of at least one layer consists of 0 to 12 mol% AgI, 0 to 50 mol% AgCl and 50 to 100% AgBr.
• the crystals are predominantly compact, for example cubic or octahedral or have transition forms. They can be characterized in that they essentially have a thickness of more than 0.2 ⁇ m. The average ratio of diameter to thickness is preferably less than 8: 1, it being true that the diameter of a grain is defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
• all or individual emulsions can also be essentially tabular Have silver halide crystals in which the ratio of diameter to thickness is greater than 8: 1.
• the emulsions can be monodisperse emulsions, which preferably have an average grain size of 0.3 ⁇ m to 1.2 ⁇ m.
• the silver halide grains can have a layered grain structure and a halide gradient.
• the emulsions can be chemically sensitized.
• the usual sensitizers are suitable for chemical sensitization of the silver halide grains.
• Sulfur-containing compounds for example allyl isothiocyanate, allyl thiourea and thiosulfates, are particularly preferred.
• Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, Z.Wiss.Phot. 46 , 65-72 (1951). It is also possible to sensitize the emulsions with polyalkylene oxide derivatives. Reference is also made to Research Disclosure No. 17 643, section III.
• the silver halide emulsions used for the materials according to the invention are negative-working silver halide emulsions. With normal exposure and color negative processing, these result in a negative image, in contrast to directly positive, veiled or unveiled emulsions.
• the emulsions can be optically sensitized in a manner known per se, e.g. with the usual polymethine dyes, such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
• polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
• Such sensitizers are from F.M. Hamer in "The Cyanine Dyes and related Compounds", (1964). In this regard, reference is made in particular to Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 18, pages 431 ff and to Research Disclosure No. 17 643, section IV, given above.
• antifoggants and stabilizers can be used.
• Particularly suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups.
• Such connections are, for example, in the article by Birr, Z.Wiss.Pho. 47 , 1952), pp. 2-58.
• Further suitable stabilizers and antifoggants are given in Research Disclosure No. 17 643 given in Section IV. Suitable compounds for improving the resistance to formalin are given in US-A 464 463.
• the recording material can also contain stabilizers for protecting the developed image, for example stabilizers against the action of visible light, UV absorbers against short-wave radiation and compounds for improving storage stability.
• stabilizers for protecting the developed image, for example stabilizers against the action of visible light, UV absorbers against short-wave radiation and compounds for improving storage stability.
• the substances are added to the multilayer structures as emulsions or in polymer form. When the color components are emulsified, they can also be dissolved directly in the oil phase of the couplers
• Suitable stabilizers against light and UV light and to improve storage stability are, for example, the following compounds
• the components of the photographic material can be incorporated using customary, known methods. If the compounds are soluble in water or alkali, they can be added in the form of aqueous solutions, optionally with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide. If they are insoluble in water or alkali, they can be incorporated into the recording materials in dispersed form in a manner known per se. For example, a solution of these compounds in a low-boiling organic solvent can be mixed directly with the silver halide emulsion or initially with an aqueous gelatin solution and the organic solvent can then be removed. The dispersion of the respective compound thus obtained can then be mixed with the silver halide emulsion. If necessary, so-called oil formers are also used, generally higher-boiling organic compounds, which include the compounds to be dispersed in the form of oily droplets.
• hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, especially gelatin, sprue aids, and plasticizers can be used.
• Proteins especially gelatin, sprue aids, and plasticizers can be used.
• 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 to harden the photographic layers with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type. Other suitable curing agents are from the German Publications 2 439 551, 2 225 230, 2 317 672 and from the above-mentioned Research Disclosure 17 643, Section XI.
• Known curing agents are, for example
• the invention further relates to a method for producing color photographic images by imagewise exposure and color development of the material according to the invention.
• Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, for example 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino-3-methyl-N-ethyl-N- ⁇ - (methanesulfonamido) ethylaniline sulfate hydrate; 4-amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate; 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N-ß-hydroxyethyl-p-phenylenediamine.
• Other useful color developers are described, for example, in J.Amer.Chem.Soc. 73 , 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979, John Wi
• the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together.
• the usual compounds can be used as bleaching agents, e.g. Fe3+ salts and Fe3+ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes etc.
• Particularly preferred are iron III complexes of aminopolycarboxylic acids, especially e.g. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
• Persulphates are also suitable as bleaching agents.
• the structure thus obtained was then hardened with a 1% strength hardening solution to such an extent that, after passing through the development process described below, the structure had a water absorption of 26 to 34 g / m 2.
• the compound H 1 was used as the curing agent.
• the layer structure thus obtained was then varied by the additives according to the invention for the protective layers b) and d) according to the table below.
• the corresponding baths have the following compositions:
• Ammonium thiosulfate (70%) 150 ml Sodium sulfite 5 g Na [Fe (EDTA)] 40 g EDTA 4 g fill up to 1 l with water

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• 1986
  • 1986-02-01 DE DE3603099A patent/DE3603099C2/de not_active Expired - Fee Related
• 1987
  • 1987-01-20 US US07/004,643 patent/US4755452A/en not_active Expired - Fee Related
  • 1987-01-21 EP EP87100781A patent/EP0231814A3/de not_active Withdrawn
  • 1987-01-30 JP JP62018747A patent/JPS62186261A/ja active Pending

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