EP0564909A1 - Process for the production of a photographic image - Google Patents
Process for the production of a photographic image Download PDFInfo
- Publication number
- EP0564909A1 EP0564909A1 EP93104864A EP93104864A EP0564909A1 EP 0564909 A1 EP0564909 A1 EP 0564909A1 EP 93104864 A EP93104864 A EP 93104864A EP 93104864 A EP93104864 A EP 93104864A EP 0564909 A1 EP0564909 A1 EP 0564909A1
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- EP
- European Patent Office
- Prior art keywords
- silver halide
- sensitive
- halide emulsion
- compounds
- color
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 0 CC(C)*(C)C(C(C)C1=O)=NN1c(cc1)ccc1S(=O)=O Chemical compound CC(C)*(C)C(C(C)C1=O)=NN1c(cc1)ccc1S(=O)=O 0.000 description 1
Classifications
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- 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
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- 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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Abstract
Description
Die Erfindung betrifft die Herstellung eines farbfotografischen Bildes durch ein sogenanntes Entwicklungs-Verstärkungsverfahren ausgehend von einem farbfotografischen Silberhalogenidmaterial mit besonderen Zwischenschichten.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.
Bei der Entwicklung farbfotografischer Aufzeichnungsmaterialien entsteht an den belichteten Stellen das Oxidationsprodukt des Entwicklers (EOP), das in der gleichen Schicht mit dem dort vorhandenen Kuppler zum gewünschten Farbstoff kuppelt (üblicherweise je nach Schicht Gelb, Purpur oder Blaugrün). Das EOP hat aber auch die Neigung, in die Nachbarschichten zu diffundieren, was zu Farbverfälschungen führt, wenn es dort auf andere Farbkuppler trifft.When developing color photographic recording materials, 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). However, the EOP also tends to diffuse into the neighboring layers, which leads to color distortions if it encounters other color couplers there.
Um dies zu verhindern, werden zwischen die lichtempfindlichen, kupplerhaltigen Silberhalogenidgelatineschichten unterschiedlicher spektraler Sensibilisierung Zwischenschichten aus Gelatine gegossen. Die Wirkung der Zwischenschichten wird üblicherweise durch den Zusatz sogenannter EOP-Fänger oder Scavenger gesteigert, worunter man Verbindungen versteht, die das EOP reduzieren. Meistens handelt es sich hierbei um dialkylsubstituierte Hydrochinone, z.B. 2,5-Dioctylhydrochinon, deren Alkylreste eine Diffusion in andere Schichten des Materials verhindern sollen und deren OH-Gruppen vom EOP oxidiert werden.To prevent this, 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. Most of the time, these are 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.
Die Menge an EOP-Fänger, die eingesetzt werden kann, ist begrenzt, da sonst erheblich dickere Zwischenschichten als gewünscht gegossen werden müßten.The amount of EOP catcher that can be used is limited, since otherwise considerably thicker intermediate layers would have to be poured than desired.
Infolgedessen ist die Farbtrennung bei Materialien, die eine ausreichende Schärfe aufweisen sollen, trotz des Einsatzes von EOP-Fängern in den Zwischenschichten, nicht ausreichend, insbesondere dann, wenn es sich um schnell entwickelbare farbfotografische Silberhalogenidmaterialien handelt. Solche sind beispielsweise Colornegativfilm, Colornegativpapier und Displaymaterial, die durch Farbverstärkungsverfahren verarbeitet werden, wobei wesentlich kürzere Farbentstehungszeiten und damit ein schnellerer Anfall hoher EOP-Konzentrationen erreicht wird.As a result, despite the use of EOP scavengers in the intermediate layers, 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.
Aufgabe der Erfindung war daher, für ein solches Entwicklungs-Verstärkungsverfahren ein Material bereitzustellen, das bei hervorragender Schärfe farbfotografische Bilder großer Farbreinheit liefert.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.
Diese Aufgabe wird dadurch gelöst, daß in den Zwischenschichten zwischen unterschiedlich sensibilisierten lichtempfindlichen Silberhalogenidemulsionsschichten Verbindungen eingesetzt werden, die in der Schicht diffusionsfest eingelagert sind und mit dem EOP unter Bindung an das EOP zu Produkten reagieren, die dem Material keine bleibende Färbung verleihen.This object is achieved in that in the intermediate layers between differently sensitized light-sensitive silver halide emulsion layers Compounds are used which are embedded in the layer in a diffusion-resistant manner and which react with the EOP to form products which do not give the material a permanent color.
Geeignete Verbindungen dieser Art sind (a) solche, die diffusionsfest machende Gruppen und wenigstens eine aktive Methylengruppe aufweisen, bei der ein Wasserstoffatom durch einen nicht abspaltbaren Rest, z.B. eine Alkylgruppe, substituiert ist, (b) solche, die eine aktive Methylengruppe aufweisen, bei der ein Wasserstoffatom durch einen abspaltbaren, eine diffusionsfest machende Gruppe enthaltenden Rest substituiert ist und das nach der Reaktion mit dem EOP entstehende Produkt keine diffusionsfest machende Gruppe mehr enthält und auswässerbar ist, oder (c) solche, die in einem Heterocyclus eine aktive Methylengruppe aufweisen, wobei nach Reaktion mit dem EOP ein farbloses Produkt entsteht.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.
Im Fall (a) entstehen nur farblose Produkte, da die Ausbildung eines Methinfarbstoffes durch den nicht abspaltbaren Substituenten verhindert wird. Im Fall (b) können auch farbige Produkte entstehen, die aber, da sie keine diffusionsfest machende Gruppe mehr enthalten, ausgewässert werden.In case (a), only colorless products are formed, since the formation of a methine dye is prevented by the non-removable substituent. In case (b), colored products can also be formed, but since they no longer contain a diffusion-proofing group, they are leached out.
Verbindungen vom Typ (a) werden auch Weißkuppler genannt.Connections of type (a) are also called white couplers.
Überraschenderweise kommt man bei Anwendung dieser Verbindungen mit sehr geringen Mengen aus, wodurch die Schichtdicke der Zwischenschicht klein gehalten werden kann.Surprisingly, the use of these compounds requires very small amounts, which means that the layer thickness of the intermediate layer can be kept small.
Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung farbfotografischen Bilder durch Verarbeitung eines farbfotografischen Silberhalogenidmaterials mit den Schritten.
- (a) Belichten,
- (b) Entwickeln mit einem Farbentwickler,
- (c) Behandeln mit H₂O₂ oder einer Verbindung, die H₂O₂ freisetzt,
- (d) Bleichen und Fixieren oder Bleichfixieren oder Fixieren, ohne zu bleichen oder Stabilisieren
- (e) gegebenenfalls Wässern und
- (f) Trocknen,
- (a) exposure,
- (b) developing with a color developer,
- (c) treating with H₂O₂ or a compound that releases H₂O₂,
- (d) bleaching and fixing or bleach-fixing or fixing without bleaching or stabilizing
- (e) optionally watering and
- (f) drying,
Von diesen Verbindungen kann jeweils eine einzige Substanz als auch eine Mischung von 2 und mehr Substanzen eingesetzt werden.A single substance as well as a mixture of two or more substances can be used in each case from these compounds.
Ebenfalls können Mischungen dieser Verbindungen mit Scavengern eingesetzt werden. Scavenger werden in Research Disclosure 17 643, Kapitel VII, 17 842 und 18 716 sowie in EP 69 070, 98 072, 124 877 und 125 522 beschrieben.Mixtures of these compounds with scavengers can also be used. 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.
Das Material kann darüberhinaus eine Substratschicht, weitere Zwischenschichten, eine oder mehrere Gelbfilterschichten und eine oder mehrere Schutz- beziehungsweise Deckschichten enthalten.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.
Die Folge der unterschiedlich sensibilisierten kupplerhaltigen Silberhalogenidemulsionsschichten ist beliebig.The consequence of the differently sensitized coupler-containing silver halide emulsion layers is arbitrary.
Bei Materialien mit mehreren Schichten gleicher Sensibilisierung müssen diese nicht notwendigerweise benachbart zueinander sein, sondern können auch in der in DE-A 2 530 645 angegebenen alternierenden Reihenfolge angeordnet sein. Bei Colornegativpapier und Displaymaterial wird üblicherweise auf dem Träger in der angegebenen Reihenfolge die blauempfindliche, die grünempfindliche und die rotempfindliche Silberhalogenidemulsionsschicht angeordnet. Eine Gelbfilterschicht entfällt dabei.In the case of materials with several layers of the same sensitization, these do not necessarily have to be adjacent to one another, but can also be arranged in the alternating order specified in DE-A 2 530 645 be. In the case of color negative paper and display material, 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.
Als Silberhalogenide der Silberhalogenidemulsionsschichten kommen AgBr, AgBrCl, AgBrI, AgBrClI und AgCl in Betracht.AgBr, AgBrCl, AgBrI, AgBrClI and AgCl come into consideration as silver halides of the silver halide emulsion layers.
Vorzugsweise enthalten die Silberhalogenide aller lichtempfindlichen Schichten wenigstens 80 Mol-% Chlorid, insbesondere 95 bis 100 Mol-% Chlorid, 0 bis 5 Mol-% Bromid und 0 bis 1 Mol-% Iodid. Die Silberhalogenidemulsionen können direkt positiv arbeitende oder vorzugsweise negativ arbeitende Emulsionen sein.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.
Bei dem Silberhalogenid kann es sich um überwiegend kompakte Kristalle handeln, die z.B. regulär kubisch oder oktaedrisch sind oder Übergangsformen aufweisen können.The silver halide can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms.
Vorzugsweise können aber auch verzwillingte, z. B. plättchenförmige Kristalle vorliegen, deren durchschnittliches Verhältnis von Durchmesser zu Dicke bevorzugt wenigstens 5:1 ist, wobei der Durchmesser eines Kornes definiert ist als der Durchmesser eines Kreises mit einem Kreisinhalt entsprechend der projizierten Fläche des Kornes. Die Schichten können aber auch tafelförmige Silberhalogenidkristalle aufweisen, bei denen das Verhältnis von Durchmesser zu Dicke größer als 5:1 ist, z.B. 12:1 bis 30:1.However, 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. However, 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.
Die Silberhalogenidkörner können auch einen mehrfach geschichteten Kornaufbau aufweisen, im einfachsten Fall mit einem inneren und einem äußeren Kornbereich (core/shell), wobei die Halogenidzusammensetzung und/oder sonstige Modifizierungen, wie z.B. Dotierungen der einzelnen Kornbereiche unterschiedlich sind. Die mittlere Korngröße der Emulsionen liegt vorzugsweise zwischen 0,2 µm und 2,0 µm, die Korngrößenverteilung kann sowohl homo- als auch heterodispers sein. Die Emulsionen können außer dem Silberhalogenid auch organische Silbersalze enthalten, z.B. Silberbenztriazolat oder Silberbehenat.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 μm and 2.0 μm, the grain size distribution can be both homo- and heterodisperse. In addition to the silver halide, the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.
Es können zwei oder mehrere Arten von Silberhalogenidemulsionen, die getrennt hergestellt werden, als Mischung verwendet werden.Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
Die fotografischen Emulsionen können nach verschiedenen Methoden (z.B. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) aus löslichen Silbersalzen und löslichen Halogeniden hergestellt werden.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.
Die Fällung des Silberhalogenids erfolgt bevorzugt in Gegenwart des Bindemittels, z.B. der Gelatine und kann im sauren, neutralen oder alkalischen pH-Bereich durchgeführt werden, wobei vorzugsweise Silberhalogenidkomplexbildner zusätzlich verwendet werden. Zu letzteren gehören z.B. Ammoniak, Thioether, Imidazol, Ammoniumthiocyanat oder überschüssiges Halogenid. Die Zusammenführung der wasserlöslichen Silbersalze und der Halogenide erfolgt wahlweise nacheinander nach dem single-jet- oder gleichzeitig nach dem double-jet-Verfahren oder nach beliebiger Kombination beider Verfahren. Bevorzugt wird die Dosierung mit steigenden Zuflußraten, wobei die "kritische" Zufuhrgeschwindigkeit, bei der gerade noch keine Neukeime entstehen, nicht überschritten werden sollte. Der pAg-Bereich kann während der Fällung in weiten Grenzen variieren, vorzugsweise wird das sogenannte pAg-gesteuerte Verfahren benutzt, bei dem ein bestimmter pAg-Wert konstant gehalten oder ein definiertes pAg-Profil während der Fällung durchfahren wird. Neben der bevorzugten Fällung bei Halogenidüberschuß ist aber auch die sogenannte inverse Fällung bei Silberionenüberschluß möglich. Außer durch Fällung können die Silberhalogenidkristalle auch durch physikalische Reifung (Ostwaldreifung), in Gegenwart von überschüssigem Halogenid und/oder Silberhalogenidkomplexierungsmittel wachsen. Das Wachstum der Emulsionskörner kann sogar überwiegend durch Ostwaldreifung erfolgen, wobei vorzugsweise eine feinkörnige, sogenannte Lippmann-Emulsion, mit einer schwerer löslichen Emulsion gemischt und auf letzterer umgelöst wird.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. In addition to the preferred precipitation with an excess of halide, so-called inverse precipitation with an excess of silver ions is also possible. In addition to precipitation, 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.
Die Fällung der Silberhalogenidkörner kann in Gegenwart von "growth modifiern" erfolgen, das sind Substanzen die das Wachstum derart beeinflussen, daß besondere Kornformen und Kornoberflächen (z.B. 111-Oberflächen bei AgCl) entstehen.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.
Ferner kann die Fällung auch in Gegenwart von Sensibilisierungsfarbstoffen erfolgen. Komplexierungsmittel und/oder Farbstoffe lassen sich zu jedem beliebigen Zeitpunkt unwirksam machen, z.B. durch Änderung des pH-Wertes oder durch eine oxidative Behandlung.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.
Als Bindemittel wird vorzugsweise Gelatine verwendet. Diese kann jedoch ganz oder teilweise durch andere synthetische, halbsynthetische oder auch natürlich vorkommende Polymere ersetzt werden. Synthetische Gelatineersatzstoffe sind beispielsweise Polyvinylalkohol, Poly-N-vinylpyrolidon, Polyacrylamide, Polyacrylsäure und deren Derivate, insbesondere deren Mischpolymerisate. Natürlich vorkommende Gelatineersatzstoffe sind beispielsweise andere Proteine wie Albumin oder Casein, Cellulose, Zucker, Stärke oder Alginate. Halbsynthetische Gelatineersatzstoffe sind in der Regel modfizierte Naturprodukte. Cellulosederivate wie Hydroxyalkylcellulose, Carboxymethylcellulose und Phthalylcellulose sowie Gelatinederivate, die durch Umsetzung mit Alkylierungs- oder Acylierungsmitteln oder durch Aufpfropfung von polymerisierbaren Monomeren erhalten worden sind, sind Beispiele hierfür.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.
Die Bindemittel sollen über eine ausreichende Menge an funktionellen Gruppen verfügen, so daß durch Umsetzung mit geeigneten Härtungsmitteln genügend widerstandsfähigen Schichten erzeugt werden können. Solche funktionellen Gruppen sind insbesondere Aminogruppen, aber auch Carboxylgruppen, Hydroxylgruppen und aktive Methylengruppen.The binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents. Such functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
Die vorzugsweise verwendete Gelatine kann durch sauren oder alkalischen Aufschluß erhalten sein. Die Herstellung solcher Gelatinen wird beispielsweise in The Science and Technology of Gelatine, herausgegeben von A.G. Ward und A. Courts, Academic Press 1977, Seite 295 ff beschrieben. Die jeweils eingesetzte Gelatine soll einen möglichst geringen Gehalt an fotografisch aktiven Verunreinigungen enthalten (Inertgelatine). Gelatinen mit hoher Viskosität und niedriger Quellung sind besonders vorteilhaft. Die Gelatine kann teilweise oder ganz oxidiert sein.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.
Nach abgeschlossener Kristallbildung oder auch schon zu einem früheren Zeitpunkt werden die löslichen Salze aus der Emulsion entfernt, z.B. durch Nudeln und Waschen, durch Flocken und Waschen, durch Ultrafiltration oder durch Ionenaustauscher.After crystal formation has been completed or at an earlier point in time, the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchangers.
Die fotografischen Emulsionen können Verbindungen zur Verhinderung der Schleierbildung oder zur Stabilisierung der fotografischen Funktion während der Produktion, der Lagerung oder der fotografischen Verarbeitung enthalten.The photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
Besonders geeignet sind Azaindene, vorzugsweise Tetra- und Pentaazaindene, insbesondere solche, die mit Hydroxyl- oder Aminogruppen substituiert sind. Derartige Verbindungen sind z. B. von Birr, Z. Wiss. Phot. 47 (1952), S. 2 - 58 beschrieben worden. Weiter können als Antischleiermittel Salze von Metallen wie Quecksilber oder Cadmium, aromatische Sulfon- oder Sulfinsäuren wie Benzolsulfinsäure, oder stickstoffhaltige Heterocyclen wie Nitrobenzimidazol, Nitroindazol, (subst.) Benztriazole oder Benzthiazoliumsalze eingesetzt werden. Geeignet sind Mercaptogruppen enthaltende Heterocyclen, z. B. Mercaptobenzthiazole, Mercaptobenzimidazole, Mercaptotetrazole, Mercaptothiadiazole, Mercaptopyrimidine, wobei diese Mercaptoazole auch eine wasserlöslichmachende Gruppe, z.B. eine Carboxylgruppe oder Sulfogruppe, enthalten können. Weitere geeignete Verbindungen sind in Research Disclosure Nr. 17643 (1978), Abschnitt VI, veröffentlicht.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. Other suitable compounds are published in Research Disclosure No. 17643 (1978), Section VI.
Die Stabilisatoren können den Silberhalogenidemulsionen vor, während oder nach deren Reifung zugesetzt werden. Selbstverständlich kann man die Verbindungen auch anderen fotografischen Schichten, die einer Halogensilberschicht zugeordnet sind, zusetzen.The stabilizers can be added to the silver halide emulsions before, during or after their ripening. Of course, the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
Es können auch Mischungen aus zwei oder mehreren der genannten Verbindungen eingesetzt werden.Mixtures of two or more of the compounds mentioned can also be used.
Die Silberhalogenidemulsionen werden üblicherweise chemisch gereift, beispielsweise durch Einwirkung von Goldverbindungen oder Verbindungen des zweiwertigen Schwefels.The silver halide emulsions are usually chemically ripened, for example by the action of gold compounds or compounds of divalent sulfur.
Die fotografischen Emulsionsschichten oder andere hydrophile Kolloidschichten des erfindungsgemäß hergestellten lichtempfindlichen Materials können oberflächenaktive Mittel für verschiedene Zwecke enthalten, wie Überzugshilfen, zur Verhinderung der elektrischen Aufladung, zur Verbesserung der Gleiteigenschaften, zum Emulgieren der Dispersion, zur Verhinderung der Adhäsion und zur Verbesserung der fotografischen Charakteristika (z.B. Entwicklungsbeschleunigung, hoher Kontrast, Sensibilisierung usw.).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.).
Geeignete Sensibilisierungsfarbstoffe sind Cyaninfarbstoffe, insbesondere der folgenden Klassen:
- 1. Rotsensibilisatoren
Dicarbocyanine mit Naphthothiazol oder Benzthiazol als basischen Endgruppen, die in 5- und/oder 6-Stellung durch Halogen, Methyl, Methoxy substituiert sein können sowie 9.11-alkylen-verbrückte, insbesondere 9.11-Neopentylenthiadicarbocyanine mit Alkyl- oder Sulfoalkylsubstituenten am Stickstoff. - 2. Grünsensibilisatoren
9-Ethyloxacarbocyanine, die in 5-Stellung durch Chlor oder Phenyl substituiert sind und am Stickstoff der Benzoxazolgruppen Alkyl- oder Sulfoalkylreste, vorzugsweise Sulfoalkylsubstituenten tragen. - 3. Blausensibilisatoren
Methincyanine mit Benzoxazol, Benzthiazol, Benzselenazol, Naphthoxazol, Naphthothiazol als basischen Endgruppen, die in 5- und/oder 6-Stellung durch Halogen, Methyl, Methoxy substituiert sein können und mindestens eine, vorzugsweise zwei, Sulfoalkylsubstituenten am Stickstoff tragen. Ferner Apomerocyanine mit einer Rhodaningruppe.
- 1. Red sensitizers
Dicarbocyanines with naphthothiazole or benzthiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy and 9.11-alkylene-bridged, in particular 9.11-neopentylene thiadicarbocyanines with alkyl or sulfoalkyl substituents on nitrogen. - 2. Green sensitizers
9-Ethyloxacarbocyanines which are substituted in the 5-position by chlorine or phenyl and carry alkyl or sulfoalkyl radicals, preferably sulfoalkyl substituents, on the nitrogen of the benzoxazole groups. - 3. Blue sensitizers
Methine cyanines with benzoxazole, benzthiazole, benzselenazole, naphthoxazole, naphthothiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy and at least one, preferably two, Wear sulfoalkyl substituents on nitrogen. Apomerocyanines with a rhodanine group.
Auf Sensibilisatoren kann verzichtet werden, wenn für einen bestimmten Spektralbereich die Eigenempfindlichkeit des Silberhalogenids ausreichend ist, beispielsweise die Blauempfindlichkeit.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.
Den unterschiedlich sensibilisierten Emulsionsschichten werden nicht diffundierende monomere oder polymere Farbkuppler zugeordnet, die sich in der gleichen Schicht oder in einer dazu benachbarten Schicht befinden können.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.
Farbkuppler zur Erzeugung des blaugrünen Teilfarbenbildes sind in der Regel Kuppler vom Phenol- oder α-Naphtholtyp.Color couplers for producing the blue-green partial color image are usually couplers of the phenol or α-naphthol type.
Farbkuppler zur Erzeugung des purpurnen Teilfarbenbildes sind in der Regel Kuppler vom Typ des 5-Pyrazolons, des Indazolons oder der Pyrazoloazole.Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type.
Farbkuppler zur Erzeugung des gelben Teilfarbenbildes sind in der Regel Kuppler mit einer offenkettigen Ketomethylengruppierung, insbesondere Kuppler vom Typ des α-Acylacetamids; geeignete Beispiele hierfür sind α-Benzoylacetanilidkuppler und α-Pivaloylacetanilidkuppler.Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the α-acylacetamide type; Suitable examples are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers.
Bei den Farbkupplern kann es sich um 4-Äquivalentkuppler, aber auch um 2-Äquivlentkuppler handeln. Letztere leiten sich von den 4-Äquivalentkupplern dadurch ab, daß sie in der Kupplungsstelle einen Substituenten enthalten, der bei der Kupplung abgespalten wird.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.
Die Kuppler enthalten üblicherweise einen Ballastrest, um eine Diffusion innerhalb des Materials, d.h. sowohl innerhalb einer Schicht oder von Schicht zu Schicht, unmöglich zu machen. Anstelle von Kupplern mit einem Ballastrest können auch hochmolekulare Kuppler eingesetzt werden.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. Instead of couplers with a ballast residue, high molecular weight couplers can also be used.
Geeignete Farbkuppler bzw. Literaturstellen, in denen solche beschrieben sind, finden sich in Research Disclosure 17 643 (1978), Kapitel VII.Suitable color couplers or literature references, in which such are described, can be found in Research Disclosure 17 643 (1978), Chapter VII.
Hochmolekulare Farbkuppler sind beispielsweise 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 beschrieben. Die hochmolekularen Farbkuppler werden in der Regel durch Polymerisation von ethylenisch ungesättigten monomeren Farbkupplern hergestellt. Sie können aber auch durch Polyaddition oder Polykondensation erhalten werden.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.
Die Einarbeitung der Kuppler oder anderer Verbindungen in Silberhalogindemulsionsschichten kann in der Weise erfolgen, daß zunächst von der betreffenden Verbindung eine Lösung, eine Dispersion oder eine Emulsion hergestellt und dann der Gießlösung für die betreffende Schicht zugefügt wird. Die Auswahl des geeigneten Lösungs- oder Dispersionsmittels hängt von der jeweiligen Löslichkeit der Verbindung ab.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.
Methoden zum Einbringen von in Wasser im wesentlichen unlöslichen Verbindungen durch Mahlverfahren sind beispielsweise in DE-A-26 09 741 und DE-A-26 09 742 beschrieben.Methods for introducing compounds which are essentially insoluble in water by grinding processes are described, for example, in DE-A-26 09 741 and DE-A-26 09 742.
Hydrophobe Verbindungen können auch unter Verwendung von hochsiedenden Lösungsmitteln, sogenannten Ölbildnern, in die Gießlösung eingebracht werden. Entsprechende Methoden sind beispielsweise in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 und EP-A-O 043 037 beschrieben.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.
Anstelle der hochsiedenden Lösungsmitteln können Oligomere oder Polymere, sogenannte polymere Ölbildner Verwendung finden.Instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
Die Verbindungen können auch in Form beladener Latices in die Gießlösung eingebracht werden. Verwiesen wird beispielsweise auf DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-A-O 014 921, EP-A-0 069 671, EP-A-O 130 115, US-A-4 291 113.The compounds can also be introduced into the casting solution in the form of loaded latices. Reference is made, for example, to DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-AO 014 921, EP-A-0 069 671, EP-AO 130 115, US Pat. A-4 291 113.
Die diffusionsfeste Einlagerung anionischer wasserlöslicher Verbindungen (z.B. von Farbstoffen) kann auch mit Hilfe von kationischen Polymeren, sogenannten Beizenpolymeren erfolgen.The diffusion-resistant incorporation of anionic water-soluble compounds (e.g. dyes) can also be carried out with the help of cationic polymers, so-called pickling polymers.
Geeignete Ölbildner sind z.B. Phthalsäurealkylester, Phosphonsäureester, Phosphorsäureester, Citronensäureester, Benzoesäureester, Amide, Fettsäureester, Trimesinsäureester, Alkohole, Phenole, Anilinderivate und Kohlenwasserstoffe.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.
Beispiele für geeignete Ölbildner sind Dibutylphthalat, Dicyclohexylphthalat, Di-2-ethylhexylphthalat, Decylphthalat, Triphenylphosphat, Tricresylphosphat, 2-Ethylhexyldiphenylphosphat, Tricyclohexylphosphat, Tri-2-ethylhexylphosphat, Tridecylphosphat, Tributoxyethylphosphat, Trichlorpropylphosphat, Di-2-ethylhexylphenylphosphat, 2-Ethylhexylbenzoat, Dodecylbenzoat, 2-Ethylhexyl-p-hydroxybenzoat, Diethyldodecanamid, N-Tetradecylpyrrolidon, Isostearylalkohol, 2,4-Di-tert.-amylphenol, Dioctylacelat, Glycerintributyrat, Isostearyllactat, Trioctylcitrat, N,N-Dibutyl-2-butoxy-5-tert.-octylanilin, Paraffin, Dodecylbenzol und Diisopropylnaphthalin.Examples of suitable oil formers are 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, N-doxy-5-butyl-2-. -octylaniline, paraffin, dodecylbenzene and diisopropylnaphthalene.
Das fotografische Material kann weiterhin UV-Licht absorbierende Verbindungen, Weißtöner, Abstandshalter, Filterfarbstoffe, Formalinfänger, Lichtschutzmittel, Antioxidantien, DMin-Farbstoffe, Zusätze zur Verbesserung der Farbstoff-, Kuppler- und Weißenstabilisierung sowie zur Verringerung des Farbschleiers, Weichmacher (Latices), Biocide und anderes enthalten.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.
UV-Licht absorbierende Verbindungen sollen einerseits die Bildfarbstoffe vor dem Ausbleichen durch UV-reiches Tageslicht schützen und andererseits als Filterfarbstoffe das UV-Licht im Tageslicht bei der Belichtung absorbieren und so die Farbwiedergabe eines Films verbessern. Üblicherweise werden für die beiden Aufgaben Verbindungen unterschiedlicher Struktur eingesetzt. Beispiele sind arylsubstituierte Benzotriazolverbindungen (US-A-3 533 794), 4-Thiazolidonverbindungen (US-A-3 314 794 und 3 352 681), Benzophenonverbindungen (JP-A-2784/71), Zimtsäureesterverbindungen (US-A-3 705 805 und 3 707 375), Butadienverbindungen (US-A-4 045 229) oder Benzoxazolverbindungen (US-A-3 700 455).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).
Es können auch ultraviolettabsorbierende Kuppler (wie Blaugrünkuppler des α-Naphtholtyps) und ultraviolettabsorbierende Polymere verwendet werden. Diese Ultraviolettabsorbentien können durch Beizen in einer speziellen Schicht fixiert sein.Ultraviolet absorbing couplers (such as α-naphthol type cyan couplers) and ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
Für sichtbares Licht geeignete Filterfarbstoffe umfassen Oxonolfarbstoffe, Hemioxonolfarbstoffe, Styrylfarbstoffe, Merocyaninfarbstoffe, Cyaninfarbstoffe und Azofarbstoffe. Von diesen Farbstoffen werden Oxonolfarbstoffe, Hemioxonolfarbstoffe und Merocyaninfarbstoffe besonders vorteilhaft verwendet.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.
Geeignete Weißtöner sind z.B. in Research Disclosure 17 643 (Dez. 1978), Kapitel V, in US-A-2 632 701, 3 269 840 und in GB-A-852 075 und 1 319 763 beschrieben.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.
Bestimmte Bindemittelschichten, insbesondere die vom Träger am weitesten entfernte Schicht, aber auch gelegentlich Zwischenschichten, insbesondere, wenn sie während der Herstellung die vom Träger am weitesten entfernte Schicht darstellen, können fotografisch inerte Teilchen anorganischer oder organischer Natur enthalten, z.B. als Mattierungsmittel oder als Abstandshalter (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dez. 1978), Kapitel XVI).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 ).
Der mittlere Teilchendurchmesser der Abstandshalter liegt insbesondere im Bereich von 0,2 bis 10 µm. Die Abstandshalter sind wasserunlöslich und können alkaliunlöslich oder alkalilöslich sein, wobei die alkalilöslichen im allgemeinen im alkalischen Entwicklungsbad aus dem fotografischen Material entfernt werden. Beispiele für geeignete Polymere sind Polymethylmethacrylat, Copolymere aus Acrylsäure und Methylmethacrylat sowie Hydroxypropylmethylcellulosehexahydrophthalat.The average particle diameter of the spacers is in particular in the range from 0.2 to 10 μm. 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. Examples of suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
Zusätze zur Verbesserung der Farbstoff-, Kuppler- und Weißenstabilität sowie zur Verringerung des Farbschleiers (Research Disclosure 17 643/1978, Kapitel VII) können den folgenden chemischen Stoffklasen angehören: Hydrochinone, 6-Hydroxychromane, 5-Hydroxycumarane, Spirochromane, Spiroindane, p-Alkoxyphenole, sterische gehinderte Phenole, Gallussäurederivate, Methylendioxybenzole, Aminophenole, sterisch gehinderte Amine, Derivate mit veresterten oder verätherten phenolischen Hydroxylgruppen, Metallkomplexe.Additives to improve dye, coupler and whiteness stability and to reduce the color fog (Research Disclosure 17 643/1978, Chapter VII) 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.
Verbindungen, die sowohl eine sterisch gehinderte Amin-Partialstruktur als auch eine sterisch gehinderte Phenol-Partialstruktur in einem Molekül aufweisen (US-A-4 268 593), sind besonders wirksam zur Verhinderung der Beeinträchtigung (Verschlechterung bzw. Abbau) von gelben Farbbildern als Folge der Entwicklung von Wärme, Feuchtigkeit und Licht. Um die Beeinträchtigung (Verschlechterung bzw. den Abbau) von purpurrroten Farbbildern, insbesondere ihre Beeinträchtigung (Verschlechterung bzw. Abbau) als Folge der Einwirkung von Licht, zu verhindern, sind Spiroindane (JP-A-159 644/81) und Chromane, die durch Hydrochinondiether oder -monoether substituiert sind (JP-A-89 835/80) besonders wirksam.Compounds that have both a hindered amine partial structure and a hindered one Phenol partial structure in a molecule (US-A-4 268 593), 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. In order to prevent the deterioration (deterioration or degradation) of crimson color images, in particular their impairment (deterioration or degradation) as a result of exposure to light, Spiroindane (JP-A-159 644/81) and chromanes are caused by Hydroquinone diethers or monoethers are particularly effective (JP-A-89 835/80).
Die Schichten des fotografischen Materials können mit den üblichen Härtungsmitteln gehärtet werden. Geeignete Härtungsmittel sind z.B. Formaldehyd , Glutaraldehyd und ähnliche Aldehydverbindungen, Diacetyl, Cyclopentadion und ähnliche Ketonverbindungen, Bis-(2-chlorethylharnstoff), 2-Hydroxy-4,6-dichlor1,3,5-triazin und andere Verbindungen, die reaktives Halogen enthalten (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 und GB-A-1 167 207) Divinylsulfonverbindungen, 5-Acetyl-1,3-diacryloylhexahydro-1,3,5-triazin und andere Verbindungen, die eine reaktive Olefinbindung enthalten (US-A-3 635 718, US-A-3 232 763 und GB-A-994 869); N-Hydroxymethylphthalimid und andere N-Methylolverbindungen (US-A-2 732 316 und US-A-2 586 168); Isocyanate (US-A-3 103 437); Aziridinverbindungen (US-A-2 725 294 und US-A-2 725 295); Verbindungen vom Carbodiimidtyp (US-A-3 100 704); Carbomoylpyridiniumsalze (DE-A-22 25 230 und DE-A-24 39 551); Carbamoyloxypyridiniumverbindungen (DE-A-24 08 814); Verbindungen mit einer Phosphor-Halogen-Bindung (JP-A-113 929/83); N-Carbonyloximid-Verbindungen (JP-A-43353/81); N-Sulfonyloximido-Verbindungen (US-A-4 111 926), Dihydrochinolinverbindungen (US-A-4 013 468), 2-Sulfonyloxypyridiniumsalze (JP-A-110 762/81), Formamidiniumsalze (EP-A-0 162 308), Verbindungen mit zwei oder mehr N-Acyloximino-Gruppen (US-A-4 052 373), Epoxyverbindungen (US-A-3 091 537), Verbindungen vom Isoxazoltyp (US-A-3 321 313 und US-A-3 543 292); Halogencarboxyaldehyde, wie Mucochlorsäure; Dioxanderivate, wie Dihydroxydioxan und Di-chlordioxan; und anorganische Härter, wie Chromalaun und Zirkonsulfat.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-A-2 586 168); Isocyanates (US-A-3 103 437); Aziridine compounds (US-A-2 725 294 and US-A-2 725 295); Carbodiimide type compounds (US-A-3 100 704); Carbomoylpyridinium salts (DE-A-22 25 230 and DE-A-24 39 551); Carbamoyloxypyridinium compounds (DE-A-24 08 814); Compounds with a phosphorus-halogen bond (JP-A-113 929/83); N-carbonyloximide compounds (JP-A-43353/81); N-sulfonyloximido compounds (US-A-4 111 926), dihydroquinoline compounds (US-A-4 013 468), 2-sulfonyloxypyridinium salts (JP-A-110 762/81), formamidinium salts (EP-A-0 162 308) , Compounds having two or more N-acyloximino groups (US-A-4 052 373), epoxy compounds (US-A-3 091 537), isoxazole-type compounds (US-A-3 321 313 and US-A-3 543 292); Halocarboxyaldehydes such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and di-chlorodioxane; and inorganic hardeners such as chrome alum and zirconium sulfate.
Die Härtung kann in bekannter Weise dadurch bewirkt werden, daß das Härtungsmittel der Gießlösung für die zu härtende Schicht zugesetzt wird, oder dadurch, daß die zu härtende Schicht mit einer Schicht überschichtet wird, die ein diffusionsfähiges Härtungsmittel enthält.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.
Unter den aufgeführten Klassen gibt es langsam wirkende und schnell wirkende Härtungsmittel sowie sogenannte Soforthärter, die besonders vorteilhaft sind. Unter Soforthärtern werden Verbindungen verstanden, die geeignete Bindemittel so vernetzen, daß unmittelbar nach Beguß, spätestens nach 24 Stunden, vorzugsweise spätestens nach 8 Stunden die Härtung so weit abgeschlossen ist, daß keine weitere durch die Vernetzungsreaktion bedingte Änderung der Sensitometrie und der Quellung des Schichtverbandes auftritt. Unter Quellung wird die Differenz von Naßschichtdicke und Trockenschichtdicke bei der wäßrigen Verarbeitung des Films verstanden (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).There are slow-acting and fast-acting hardeners and so-called instant hardeners, which are particularly advantageous, in the classes listed. 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).
Bei diesen mit Gelatine sehr schnell reagierenden Härtungsmitteln handelt es sich z.B. um Carbamoylpyridiniumsalze, die mit freien Carboxylgruppen der Gelatine zu reagieren vermögen, so daß letztere mit freien Aminogruppen der Gelatine unter Ausbildung von Peptidbindungen und Vernetzung der Gelatine reagieren.These 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.
Es gibt diffusionsfähige Härtungsmittel, die auf alle Schichten innerhalb eines Schichtverbandes in gleicher Weise härtend wirken. Es gibt aber auch schichtbegrenzt wirkende, nicht diffundierende, niedermolekulare und hochmolekulare Härter. Mit ihnen kann man einzelnen Schichten, z.B. die Schutzschicht besonders stark vernetzen. Dies ist wichtig, wenn man die Silberhalogenid-Schicht wegen der Silberdeckkrafterhöhung wenig härtet und mit der Schutzschicht die mechanischen Eigenschaften verbessern muß (EP-A 0 114 699).There are diffusible curing agents that have the same curing effect on all layers within a layer structure. There are also layer-limited, non-diffusing, low-molecular and high-molecular hardeners. They can be used to separate individual layers, e.g. crosslink the protective layer particularly strongly. This is important if the silver halide layer is hardened little because of the increase in silver opacity and the protective layer has to improve the mechanical properties (EP-A 0 114 699).
Erfindungsgemäß verwendbare Weißkuppler sind beispielsweise aus DE-OS 19 09 067 und 27 05 974 bekannt.White couplers which can be used according to the invention are known, for example, from DE-OS 19 09 067 and 27 05 974.
Besonders geeignete erfindungsgemäße Verbindungen vom Typ (a) entsprechen der Formel
worin
- R₁ und R₃
- übliche Kupplersubstituenten sind, von denen wenigstens einer eine Ballastfunktion aufweist, und
- R₂
- eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 6 C-Atomen ist.
wherein
- R₁ and R₃
- are usual coupler substituents, at least one of which has a ballast function, and
- R₂
- is a straight-chain or branched alkyl group with 1 to 6 carbon atoms.
Vorzugsweise sind R₁ eine R₄-NH-Gruppe, R₃ eine R₅-SO₂-Gruppe, R₄ eine Acylgruppe mit Ballastfunktion und R₅ C₁-C₃-Alkyl.Preferably R₁ is an R₄-NH group, R₃ an R₅-SO₂ group, R₄ an acyl group with ballast function and R₅ C₁-C₃-alkyl.
Beispiele für derartige Weißkuppler sind
x = 25, y = 67 und z = 8 Gewichtsprozent
x = 20, y = 70 und z = 10 Gewichtsprozent
x = 18, y = 75 und z = 7 Gew.-%.
x = 20, y = 10, y' = 60, z = 10 Gewichtsprozent
Verbindungen vom Typ (b) entsprechen der Formel
A - Bm
wobei
- A
- der Rest einer zur Reaktion mit EOP befähigten Verbindung ist, der keine diffusionsfest machende Gruppe aufweist und nach Substitution von Bm durch den Rest des EOP leicht ausgewässert wird, vorzugsweise eine 1,3-Dicarbonylverbindung, eine 1,3-dicarbonylanaloge Verbindung, oder ein elektronenreicher Aromat, z.B. β-Ketocarbonsäurederivate, Pyrazolone, Pyrazoloazole, Phenole und Naphthole,
- B
- eine funktionelle, mit EOP von A abspaltbare Gruppe, die wenigstens einen diffusionsfest machenden Substituenten aufweist, und
- m
- eine Zahl ≧1 bedeuten.
x = 25, y = 67 and z = 8 percent by weight
x = 20, y = 70 and z = 10 percent by weight
x = 18, y = 75 and z = 7% by weight.
x = 20, y = 10, y '= 60, z = 10 percent by weight
Compounds of type (b) correspond to the formula
A - B m
in which
- A
- the remainder of a compound capable of reacting with EOP, which has no diffusion-proofing group and, after substitution of B m by the rest of the EOP, is slightly leached out, preferably a 1,3-dicarbonyl compound, a 1,3-dicarbonyl-analogue compound, or a electron-rich aromatic, for example β-ketocarboxylic acid derivatives, pyrazolones, pyrazoloazoles, phenols and naphthols,
- B
- a functional group which can be split off from A using EOP and which has at least one diffusion-resistant substituent, and
- m
- mean a number ≧ 1.
Beispiele sind
Verbindungen vom Typ (c) entsprechen der Formel
worin
- X
- O, S oder NR
- R
- H oder Alkyl und
- Q
- die restlichen Glieder zur Bildung eines mono- oder bicyclischen Heterocyclus bedeuten.
Compounds of type (c) correspond to the formula
wherein
- X
- O, S or NR
- R
- H or alkyl and
- Q
- the remaining members to form a mono- or bicyclic heterocycle.
Beispiele sind
Ob man bei der Verarbeitung auf das Bleichen des entwickelten Silbers verzichten kann, hängt von der Menge des erzeugten Silbers, von den Anforderungen an die Bildqualität und vom Anwendungsgebiet des Materials ab.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.
Entwicklung und Verstärkung können einbadig oder zweibadig erfolgen, wobei vorzugsweise die Konzentrationen an Farbentwickler 0,01 bis 0,1 mol/l und an H₂O₂ 0,5 bis 25 g/l betragen.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.
Dem Entwickeln, Verstärken, Bleichfixieren oder Fixieren beziehungsweise Stabilisieren können sich die üblichen Schritte Wässern und Trocknen anschließen, Auch das Fixieren (Lösen des unbelichteten Silberhalogenids) kann entfallen, wenn das Silberhalogenid durch ein Stabilisierbad in ein licht-unempfindliches Silberkomplexsalz überführt wird. In diesem Fall kann sich an die Stabilisierung sofort die Trocknung anschließen.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.
Als Farbentwicklerverbindung lassen sich sämtliche Entwicklerverbindungen verwenden, die die Fähigkeit besitzen, in Form ihres Oxidationsproduktes mit Farbkupplern zu Azomethin- beziehungsweise Indophenolfarbstoffen zu reagieren. Geeignete Farbentwicklerverbindungen sind aromatische, mindestens eine primäre Aminogruppe enthaltende Verbindungen vom p-Phenyldiamintyp, beispielsweise N,N-Dialkyl-p-phenylendiamine wie N,N-Diethyl-p-phenylendiamin, 1-(N-Ethyl-N-methansulfon-amidoethyl)-3-methyl-p-phenylendiamin, 1-(N-Ethyl-N-hydroxyethyl)-3-methyl-p-phenylendiamin, 1-(N-Ethyl-N-(3-hydroxypropyl)-3-methyl-p-phenylendiamin und 1-(N-Ethyl-N-methoxyethyl)-3-methyl-p-phenylendiamin. Weitere brauchbare Farbentwickler sind beispielsweise in J. Amer. Chem. Soc. 73, 3106 (1951) und G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, Seite 545 ff. beschrieben.All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound. 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, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing , 1979, John Wiley and Sons, New York, page 545 ff.
Ein farbfotografisches Aufzeichnungsmaterial wurde hergestellt, indem auf einen Schichtträger aus beidseitig mit Polyethylen beschichtetem Papier die folgenden Schichten in der angegebenen Reihenfolge aufgetragen wurden. Die Mengenangaben beziehen sich jeweils auf 1 m². Für den Silberhalogenidauftrag werden die entsprechenden Mengen AgNO₃ angegeben.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. For the silver halide application, the corresponding amounts of AgNO₃ are given.
- 1. Schicht (Substratschicht):
0,2 g Gelatine - 2. Schicht (blauempfindliche Schicht):
blauempfindliche Silberhalogenidemulsion
(99,5 Mol.-% Chlorid, 0,5 Mol.-% Bromid, mittlerer Korndurchmesser 0,8 µm) aus 0,4 g AgNO₃ mit
1,04 g Gelatine
0,60 g Gelbkuppler GB 1
0,01 g Weißkuppler W 7
0,40 g Trikresylphosphat (TKP) - 3. Schicht (Schutzschicht):
1,1 g Gelatine
x mmol Scavenger SC 1
y mmol Weißkuppler W7 - 4. Schicht (grünempfindliche Schicht)
grünsensibilisierte Silberhalogenidemulsion
(100 Mol.-% Chlorid, mittlerer Korndurchmesser 0,4 µm) aus 0,38 g AgNO₃ mit
1,05 g Gelatine
0,40 g Purpurkuppler PP 1
0,06 g 2,5-Dioctylhydrochinon
0,45 g Dibutylphthalat (DBP)
0,40 g TKP - 5. Schicht (UV-Schutzschicht)
1,30 g Gelatine
0,60 g UV-Absorber UV 1
x mmol Scavenger SC 1
y mmol Weißkuppler W7 - 6. Schicht (rotempfindliche Schicht)
rotsensibilisierte Silberhalogenidemulsion
(100 Mol.-% Chlorid, mittlerer Korndurchmesser 0,35 µm) aus 0,28 g AgNO₃ mit
0,72 g Gelatine
0,36 g Blaugrünkuppler BG 1
0,36 g TKP - 7. Schicht (UV-Schutzschicht)
0,35 g Gelatine
0,15 g UV-Absorber UV 1
0,075g TKP - 8. Schicht (Schutzschicht)
0,9 g Gelatine
0,3 g Härtungsittel H 1
Die Schichten wurden getrocknet, in einem Sensitometer durch einen Stufenkeil mit 120 Lx.s hinter Grün- beziehungsweise Rotfilter bildmäßig belichtet und wie folgt entwickelt:
- 1st layer (substrate layer):
0.2 g gelatin - 2nd layer (blue-sensitive layer):
blue sensitive silver halide emulsion
(99.5 mol .-% chloride, 0.5 mol .-% bromide, average grain diameter 0.8 microns) from 0.4 g of AgNO₃ with
1.04 g of gelatin
0.60 g yellow coupler GB 1
0.01 g white coupler W 7
0.40 g tricresyl phosphate (CPM) - 3rd layer (protective layer):
1.1 g gelatin
x mmol Scavenger SC 1
y mmol white coupler W7 - 4th layer (green-sensitive layer)
green-sensitized silver halide emulsion
(100 mol% chloride, average grain diameter 0.4 µm) from 0.38 g of AgNO₃ with
1.05 g gelatin
0.40 g purple coupler PP 1
0.06 g 2,5-dioctylhydroquinone
0.45 g dibutyl phthalate (DBP)
0.40 g CPM - 5th layer (UV protective layer)
1.30 g gelatin
0.60 g UV absorber UV 1
x mmol Scavenger SC 1
y mmol white coupler W7 - 6th layer (red-sensitive layer)
red-sensitized silver halide emulsion
(100 mol% chloride, average grain diameter 0.35 µm) from 0.28 g AgNO₃ with
0.72 g gelatin
0.36 g blue-green coupler BG 1
0.36 g CPM - 7th layer (UV protective layer)
0.35 g gelatin
0.15 g UV absorber UV 1
0.075g CPM - 8th layer (protective layer)
0.9 g gelatin
0.3 g of curing agent H 1
The layers were dried, exposed imagewise in a sensitometer through a step wedge with 120 Lx.s behind the green or red filter and developed as follows:
Bei den verarbeiteten und getrockneten Proben wurde der Purpur- und Blaugrünauszug jeweils hinter Blau-, Grün- und Rotfilter gemessen und die prozentualen Nebendichten bei den Dichten 0,6, 1,0 und 1,5 über Schleier bestimmt. Aus der Tabelle ist zu ersehen, daß die Nebendichte mit steigendem Scavenger- oder Weißkupplerauftrag geringer werden. Weiter ist der Tabelle zu entnehmen, daß Weißkuppler wesentlich effektiver ist als der Scavenger. Bei Verwendung von Weißkuppler im Vergleich zum Scavenger läßt sich demnach der Auftrag erheblich reduzieren, ohne die Farbreinheit zu verschlechtern.In the processed and dried samples, 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.
Claims (3)
R₁ und R₃ übliche Kupplersubstituenten sind, von denen wenigstens einer eine Ballastfunktion aufweist, und
R₂ eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 6 C-Atomen ist.Process according to Claim 1, characterized in that white couplers of the formula are used as compounds which are embedded in the layer in a diffusion-resistant manner and react with the oxidation product of the developer while binding to the oxidation product of the developer to give products which do not impart any permanent color to the material
R₁ and R₃ are common coupler substituents, at least one of which has a ballast function, and
R₂ is a straight-chain or branched alkyl group with 1 to 6 carbon atoms.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4211460A DE4211460A1 (en) | 1992-04-06 | 1992-04-06 | Method for producing a photographic image |
DE4211460 | 1992-04-06 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0564909A1 true EP0564909A1 (en) | 1993-10-13 |
EP0564909B1 EP0564909B1 (en) | 1998-09-02 |
Family
ID=6456170
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93104864A Expired - Lifetime EP0564909B1 (en) | 1992-04-06 | 1993-03-24 | Process for the production of a photographic image |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0564909B1 (en) |
JP (1) | JPH0619095A (en) |
DE (2) | DE4211460A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE1009091A3 (en) * | 1995-01-24 | 1996-11-05 | Agfa Gevaert Ag | Material for the silver halide color photography. |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0207400A2 (en) * | 1985-06-29 | 1987-01-07 | Agfa-Gevaert AG | Photographic recording material with a particular stability and process for preparing photographic images |
EP0358037A2 (en) * | 1988-09-03 | 1990-03-14 | Agfa-Gevaert AG | Method for processing a colour-photographic material |
EP0447656A1 (en) * | 1990-03-22 | 1991-09-25 | Agfa-Gevaert AG | Silver halide colour photographic material and its developing process |
EP0464409A1 (en) * | 1990-06-23 | 1992-01-08 | Agfa-Gevaert AG | Colour photographic recording material |
EP0526795A1 (en) * | 1991-08-03 | 1993-02-10 | Agfa-Gevaert AG | Process for the production of a photographic image |
-
1992
- 1992-04-06 DE DE4211460A patent/DE4211460A1/en not_active Withdrawn
-
1993
- 1993-03-24 DE DE59308939T patent/DE59308939D1/en not_active Expired - Fee Related
- 1993-03-24 EP EP93104864A patent/EP0564909B1/en not_active Expired - Lifetime
- 1993-04-06 JP JP5101887A patent/JPH0619095A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0207400A2 (en) * | 1985-06-29 | 1987-01-07 | Agfa-Gevaert AG | Photographic recording material with a particular stability and process for preparing photographic images |
EP0358037A2 (en) * | 1988-09-03 | 1990-03-14 | Agfa-Gevaert AG | Method for processing a colour-photographic material |
EP0447656A1 (en) * | 1990-03-22 | 1991-09-25 | Agfa-Gevaert AG | Silver halide colour photographic material and its developing process |
EP0464409A1 (en) * | 1990-06-23 | 1992-01-08 | Agfa-Gevaert AG | Colour photographic recording material |
EP0526795A1 (en) * | 1991-08-03 | 1993-02-10 | Agfa-Gevaert AG | Process for the production of a photographic image |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE1009091A3 (en) * | 1995-01-24 | 1996-11-05 | Agfa Gevaert Ag | Material for the silver halide color photography. |
Also Published As
Publication number | Publication date |
---|---|
JPH0619095A (en) | 1994-01-28 |
EP0564909B1 (en) | 1998-09-02 |
DE4211460A1 (en) | 1993-10-07 |
DE59308939D1 (en) | 1998-10-08 |
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