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
  • G03C7/39208—Organic compounds
  • G03C7/3924—Heterocyclic
  • G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
  • G03C7/39252—Heterocyclic the nucleus containing only nitrogen as hetero atoms two nitrogen atoms
• • 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
  • G03C7/3017—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction
  • G03C7/302—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction using peroxides

Definitions

• the invention relates to the production of a color photographic image by a so-called development enhancement process starting from a color photographic silver halide material with special intermediate layers.
• the oxidation product of the developer (EOP) is formed in the exposed areas, which couples in the same layer with the coupler present there to form the desired dye (usually yellow, purple or cyan, depending on the layer).
• the EOP also tends to diffuse into the neighboring layers, which leads to color distortions if it encounters other color couplers there.
• intermediate layers of gelatin are cast between the light-sensitive, coupler-containing silver halide gelatin layers of different spectral sensitization.
• the effect of the intermediate layers is usually due to the addition so-called EOP catcher or scavenger increased, which means compounds that reduce the EOP.
• EOP catcher or scavenger increased, which means compounds that reduce the EOP.
• dialkyl-substituted hydroquinones for example 2,5-dioctylhydroquinone, whose alkyl residues are intended to prevent diffusion into other layers of the material and whose OH groups are oxidized by the EOP.
• EOP catcher that can be used is limited, since otherwise considerably thicker intermediate layers would have to be poured than desired.
• the color separation is not sufficient for materials which are said to have sufficient sharpness, particularly when it is a matter of rapidly developing color photographic silver halide materials.
• examples of these are color negative film, color negative paper and display material, which are processed by color intensification processes, with significantly shorter color formation times and thus a faster occurrence of high EOP concentrations being achieved.
• the object of the invention was therefore to provide a material for such a development amplification process which, with outstanding sharpness, delivers color photographic images of great color purity.
• Suitable compounds of this type are (a) those which have diffusion-proofing groups and at least one active methylene group in which a hydrogen atom is replaced by a non-removable group, e.g. an alkyl group which is substituted, (b) those which have an active methylene group in which a hydrogen atom is substituted by a cleavable radical which contains a diffusion-proofing group and the product formed after the reaction with the EOP no longer contains any diffusion-proofing group and can be washed out, or (c) those which have an active methylene group in a heterocycle, a colorless product being formed after reaction with the EOP.
• Connections of type (a) are also called white couplers.
• a single substance as well as a mixture of two or more substances can be used in each case from these compounds.
• Scavengers are described in Research Disclosure 17 643, Chapter VII, 17 842 and 18 716 and in EP 69 070, 98 072, 124 877 and 125 522.
• the material can also contain a substrate layer, further intermediate layers, one or more yellow filter layers and one or more protective or cover layers.
• the blue-sensitive, the green-sensitive and the red-sensitive silver halide emulsion layer are usually arranged on the support in the order given. There is no yellow filter layer.
• AgBr, AgBrCl, AgBrI, AgBrClI and AgCl come into consideration as silver halides of the silver halide emulsion layers.
• the silver halides of all light-sensitive layers preferably contain at least 80 mol% of chloride, in particular 95 to 100 mol% of chloride, 0 to 5 mol% of bromide and 0 to 1 mol% of iodide.
• the silver halide emulsions can be directly positive-working or preferably negative-working emulsions.
• the silver halide can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms.
• twins e.g. B. are platelet-shaped crystals
• the average ratio of diameter to thickness is preferably at least 5: 1, wherein 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.
• the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is greater than 5: 1, for example 12: 1 to 30: 1.
• the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different.
• the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be both homo- and heterodisperse.
• the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.
• Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
• the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
• various methods e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
• the silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used.
• the latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide.
• the water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded.
• the pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation.
• so-called inverse precipitation with an excess of silver ions is also possible.
• the silver halide crystals can also grow through physical ripening (Ostwald ripening), in the presence of excess halide and / or silver halide complexing agent.
• the growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.
• the silver halide grains can be precipitated in the presence of "growth modifiers", which are substances which influence growth in such a way that special grain shapes and grain surfaces (for example 111 surfaces in AgCl) are formed.
• growth modifiers are substances which influence growth in such a way that special grain shapes and grain surfaces (for example 111 surfaces in AgCl) are formed.
• the precipitation can also be carried out in the presence of sensitizing dyes.
• Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.
• Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers.
• Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers.
• Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates.
• Semi-synthetic gelatin substitutes are usually modified natural products.
• Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose as well as gelatin derivatives which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers are examples of this.
• the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
• functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
• the gelatin which is preferably used can be obtained by acidic or alkaline digestion.
• the production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff.
• the gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
• the gelatin can be partially or completely oxidized.
• the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchangers.
• the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
• Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups.
• Such connections are e.g. B. von Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58.
• Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles can also be used as antifoggants such as nitrobenzimidazole, nitroindazole, (subst.) benzotriazoles or benzothiazolium salts.
• Heterocycles containing mercapto groups e.g. B.
• mercaptobenzthiazoles mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, these mercaptoazoles also containing a water-solubilizing group, for example a carboxyl group or sulfo group.
• a water-solubilizing group for example a carboxyl group or sulfo group.
• the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
• the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
• the silver halide emulsions are usually chemically ripened, for example by the action of gold compounds or compounds of divalent sulfur.
• the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (e.g. acceleration of development, high contrast, sensitization etc.).
• surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (e.g. acceleration of development, high contrast, sensitization etc.).
• Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the sensitivity to blue.
• the differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it.
• Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type.
• Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type.
• Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the ⁇ -acylacetamide type; Suitable examples are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers.
• the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
• the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site, which is split off during the coupling.
• the couplers usually contain a ballast residue to prevent diffusion within the material, i.e. both within a layer or from layer to layer, to make impossible.
• a ballast residue instead of couplers with a ballast residue, high molecular weight couplers can also be used.
• High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211.
• the high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
• the couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question.
• the selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
• Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-O 043 037.
• oligomers or polymers instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
• the compounds can also be introduced into the casting solution in the form of loaded latices.
• anionic water-soluble compounds e.g. dyes
• pickling polymers e.g. acrylic acid
• Suitable oil formers are, for example, alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
• oil formers examples include dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phylate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert-amylphenol, dioctyl acylate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N,
• the photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides and others.
• Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film.
• Connections of different structures are usually used for the two tasks. Examples are aryl substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or benzoxazole compounds (US-A-3,700,455).
• Ultraviolet absorbing couplers such as ⁇ -naphthol type cyan couplers
• ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
• Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
• Suitable white toners are e.g. in Research Disclosure 17,643 (Dec. 1978), Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.
• Certain layers of binder particularly the layer furthest from the backing, but also occasionally intermediate layers, especially if they are the furthest from the backing during manufacture represent removed layer, can contain photographically inert particles of inorganic or organic nature, for example as matting agents or as spacers (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI ).
• the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
• the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath.
• suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
• Additives to improve dye, coupler and whiteness stability and to reduce the color fog can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes, p- Alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
• Compounds that have both a hindered amine partial structure and a hindered one Phenol partial structure in a molecule are particularly effective for preventing the deterioration (deterioration or degradation) of yellow color images as a result of the development of heat, moisture and light.
• Spiroindane JP-A-159 644/81
• chromanes are caused by Hydroquinone diethers or monoethers are particularly effective (JP-A-89 835/80).
• the layers of the photographic material can be hardened with the usual hardening agents.
• Suitable curing agents include formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethyl urea), 2-hydroxy-4,6-dichloro 1,3,5-triazine and other compounds containing reactive halogen ( US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207) divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732 316 and US
• the hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
• Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that hardening is completed to the extent that no further change in the sensitometry and the Swelling of the layer structure occurs. Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
• hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.
• White couplers which can be used according to the invention are known, for example, from DE-OS 19 09 067 and 27 05 974.
• R1 is an R4-NH group, R3 an R5-SO2 group, R4 an acyl group with ballast function and R5 C1-C3-alkyl.
• Whether one can do without bleaching the developed silver during processing depends on the amount of silver produced, the requirements for image quality and the field of application of the material.
• Development and reinforcement can take place in one or two baths, the concentrations of color developer preferably being 0.01 to 0.1 mol / l and H2O2 being 0.5 to 25 g / l.
• Developing, strengthening, bleach-fixing or fixing or stabilizing can be followed by the usual steps of washing and drying.Fixing (dissolving the unexposed silver halide) can also be omitted if the silver halide is converted into a light-insensitive silver complex salt by a stabilizing bath. In this case, the drying can immediately follow the stabilization.
• Suitable color developer compounds are aromatic compounds of the p-phenyldiamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfone-amidoethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl-N- (3-hydroxypropyl) -3-methyl-p- phenylene diamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylene diamine Further useful color developers are described
• a color photographic recording material was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene.
• the quantities given relate to 1 m2.
• the corresponding amounts of AgNO3 are given.
• the purple and teal extracts were measured behind the blue, green and red filters, and the percentage secondary densities at the densities 0.6, 1.0 and 1.5 were determined using fog. From the table it can be seen that the secondary density decreases with increasing scavenger or white coupler application. The table also shows that white couplers are much more effective than the scavenger. When using white couplers compared to the scavenger, the order can be reduced considerably without reducing the color purity.

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

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Citations (5)

• 1992
  • 1992-04-06 DE DE4211460A patent/DE4211460A1/de not_active Withdrawn
• 1993
  • 1993-03-24 DE DE59308939T patent/DE59308939D1/de not_active Expired - Fee Related
  • 1993-03-24 EP EP93104864A patent/EP0564909B1/fr not_active Expired - Lifetime
  • 1993-04-06 JP JP5101887A patent/JPH0619095A/ja active Pending

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