EP0437818A2 - Colour photographic recording material - Google Patents
Colour photographic recording material Download PDFInfo
- Publication number
- EP0437818A2 EP0437818A2 EP90125261A EP90125261A EP0437818A2 EP 0437818 A2 EP0437818 A2 EP 0437818A2 EP 90125261 A EP90125261 A EP 90125261A EP 90125261 A EP90125261 A EP 90125261A EP 0437818 A2 EP0437818 A2 EP 0437818A2
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- EP
- European Patent Office
- Prior art keywords
- color
- compounds
- alkyl
- silver halide
- couplers
- 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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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
- G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
- G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
- G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
- G03C7/30535—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site not in rings of cyclic compounds
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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
- G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
- G03C7/3882—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific polymer or latex
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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
- G03C7/396—Macromolecular additives
Definitions
- the invention relates to a color photographic recording material having at least one silver halide emulsion layer and a diffusion-resistant ⁇ -acylacetanilide yellow coupler, the anilide group of which is substituted by an N-acylsulfamoyl group which is dissolved in a specific organic solvent.
- the coupling speed of the color couplers with the oxidation product of the color developer should be as high as possible and the highest possible color density should be achieved.
- the color couplers and the dyes obtained from them must be sufficiently stable to light, elevated temperature and moisture. This applies to both fresh material and processed material. For example, the remaining coupler still present in the image whites of the processed material must not turn yellow.
- the dyes should be sufficiently resistant to gaseous reducing or oxidizing agents. They must also be firmly anchored in the image layer and should separate as fine a grain as possible during the chromogenic development.
- the dyes resulting from the color couplers in the chromogenic development must have a favorable absorption curve with a maximum that corresponds to the color of the desired partial image and the lowest possible secondary absorptions.
- An aliphatic radical represented by Y is preferably a tert-alkyl radical, in particular tert-butyl.
- a cycloaliphatic radical represented by Y is, for example, a cyclohexyl, norbornyl or adamantyl radical.
- a group represented by X on color coupling is preferably a cyclic group linked via an oxygen atom or via a nitrogen atom, in particular a ring nitrogen atom, e.g. an optionally substituted 5- or 6-membered heterocyclic ring linked via a ring nitrogen atom.
- Such cleavable groups also referred to as escape groups, usually give the coupler the behavior of a 2-equivalent coupler, i.e. the coupler only requires half as much developable silver halide for color coupling as the corresponding 4-equivalent coupler, in which X denotes a hydrogen atom.
- the refugee groups also include those that are photographically effective and, for example, inhibit or accelerate development.
- the couplers are known from US-A-4 617 256.
- the couplers of the formula (I) have the disadvantage that the dyes produced from them with the customary color developers of the p-phenylenediamine series have unsatisfactory lightfastness.
- these couplers are sparingly soluble in common solvents such as tricresyl phosphate, which leads to crystalline precipitations and thus to casting errors (so-called point errors).
- the object of the invention was therefore to remedy these disadvantages without the positive properties of this coupler class being lost.
- the invention therefore relates to a color photographic recording material having at least one silver halide emulsion layer and a diffusion-resistant coupler of the formula (I), characterized in that liquid ester-containing compounds which have a molecular weight of at least 350 are used as oil formers for the color couplers of the formula (I).
- the oil formers are preferably mono- or diesters of aliphatic or aromatic dicarboxylic acids and aliphatic or araliphatic alcohols or polyesters of aliphatic or aromatic dicarboxylic acids and aliphatic diols.
- the molecular weight preferably does not exceed 1200.
- Suitable oil formers are, for example, dinonyl adipate, dinonyl phthalate, octadecylene succinic acid monobenzyl ester and polymers of adipic acid or phthalic acid and diols, for example butanediol and / or pentanediol.
- Up to 30% by weight of the oil binder can be replaced by other oil formers, for example tricresyl phosphate or polyalkylene glycols.
- the yellow couplers are only released in the oil former according to the invention.
- the diffusion-resistant yellow couplers of the present invention are incorporated into the casting solution of the silver halide emulsion layers or other colloid layers in the oil formers according to the invention, if appropriate in the presence of a wetting or dispersing agent.
- the hydrophilic casting solution can of course contain other conventional additives in addition to the binder.
- the color coupler solution does not need to be directly dispersed in the casting solution for the silver halide emulsion layer or other water permeable layer; Rather, it can also be advantageously first dispersed in an aqueous non-photosensitive solution of a hydrophilic colloid, whereupon the mixture obtained is mixed with the coating solution for the photosensitive silver halide emulsion layer or another water-permeable layer before application.
- Suitable light-sensitive silver halide emulsions are emulsions of silver chloride, silver bromide or mixtures thereof, possibly with a low silver iodide content of up to 10 mol% in one of the commonly used hydrophilic binders.
- Gelatin is preferably used as the binder for the photographic layers used. However, this can be replaced in whole or in part by other natural or synthetic binders.
- the advantages according to the invention become particularly clear when the color material according to the invention contains only silver halide emulsion with at least 95 mol% silver chloride in the light-sensitive layers.
- the emulsions can be chemically and spectrally sensitized in the usual way.
- the light-sensitive layer to which the yellow coupler according to the invention is assigned is in particular blue-sensitized.
- the color photographic material which preferably contains a reflective support, also contains at least one green-sensitive layer to which a magenta coupler is assigned and at least one red-sensitive layer to which a cyan coupler is assigned, and optionally intermediate and protective layers.
- 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 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products.
- the 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue (e.g. DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, e.g. as a development inhibitor or accelerator.
- Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
- Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type.
- Color coupler for generating the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type.
- the blue-green and purple couplers can be incorporated in the same way and with the same oil formers as the yellow couplers.
- Suitable oil formers for magenta and cyan couplers are in addition other alkyl phthalates, phosphonic 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 non-light-sensitive intermediate layers which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products prevent from one photosensitive to another photosensitive layer with different spectral sensitization.
- Suitable agents which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), Chapter VII, 17 842/1979, pages 94-97 and 18.716 / 1979, page 650 and in EP-A- 69,070, 98,072, 124,877, 125,522 and in US-A-463,226.
- the silver halide present as a light-sensitive component in the photographic material can be predominantly compact crystals, which are e.g. are regular cubic or octahedral or can have transitional forms.
- platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being 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 substantially greater than 5: 1, e.g. 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 doping of the individual grain areas, being different.
- the middle The 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. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%.
- the emulsions can also contain organic silver salts, for example 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.
- Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe can also be present during the precipitation and / or physical ripening of the silver halide grains.
- 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, for example by changing the pH or by an oxidative treatment.
- 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 silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog have been reached.
- the procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).
- Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (for example gold, platinum, palladium, iridium).
- Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic compounds can also be used Nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia of Industrial Chemistry, 4th edition, vol. 18, pp. 431 ff. and Research Disclosure No. 17643, Section III).
- reduction sensitization with the addition of reducing agents can be carried out by hydrogen, by low pAg (for example less than 5) and / or high pH (for example above 8).
- 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 for example from 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 such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can also be used as antifoggants.
- metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can also be used as antifoggants.
- Heterocycles containing mercapto groups for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
- mercaptobenzthiazoles for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines
- these mercaptoazoles also being able to contain 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 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 (eg acceleration of development, high contrast, sensitization etc.).
- non-ionic surfactants for example alkylene oxide compounds, glycerol compounds or glycidol compounds
- cationic surfactants for example higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds
- sulfonium compounds or phosphonium compounds anionic surfactants containing an acid group, for example carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group
- ampholytic surfactants for example amino acid and aminosulfonic acid compounds and sulfur or phosphoric acid esters of an amino alcohol.
- 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.
- 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).
- binder layers in particular the layer furthest away from the carrier, but also occasionally intermediate layers, especially if they represent the layer furthest away from the carrier during production, can contain photographically inert particles of an inorganic or organic nature, e.g. 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.
- the layers of the photographic material can be hardened with the usual hardening agents.
- Suitable curing agents are, for example, 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, the reactive halogen included (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 7
- 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 the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry caused by the crosslinking reaction 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.
- Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step.
- 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-phenylenediamine 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-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
- 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.
- bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used.
- Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
- Persulphates and peroxides e.g. Hydrogen peroxide.
- the bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.
- the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent.
- this stabilizing bath also functions as a final bath.
- a protective layer of 0.9 g / m2 of gelatin and 0.3 g / m2 of the hardening agent of the formula was applied to this layer applied and the samples dried.
- the samples were exposed behind a grayscale wedge, developed in the color developer specified below, then fixed to bleach, washed and dried.
- Coupler V1 has the formula: It turns out that when DBP is used the lightfastness of the dye formed is worse than with oil formers according to the invention, that when using DLA disadvantages in tropical stability occur and that the comparative coupler V1 shows low sensitivity, poor dark fading stability and poor tropical stability even in solvents according to the invention .
- TKP is comparable to the oil formers according to the invention with regard to the sensitometric properties, but shows an increased number of pouring errors compared to the samples according to the invention, which is shown in Example 2.
- Samples 4 to 11 are according to the invention.
- the emulsifier stability was checked by counting punctiform yellow coupler deposits / m2 on the cast material, with a freshly prepared coupler solution ("fresh”) and a coupler solution stored at 40 ° C for 24 hours (“ stored ”) were used. The results are shown in Table 2.
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Abstract
Description
Die Erfindung betrifft ein farbfotografisches Aufzeichnungsmaterial mit mindestens einer Silberhalogenidemulsionsschicht und einem diffusionsfesten α-Acylacetanilid-Gelbkuppler, dessen Anilidgruppe mit einer N-Acylsulfamoylgruppe substituiert ist, der in einem bestimmten organischen Lösungsmittel gelöst ist.The invention relates to a color photographic recording material having at least one silver halide emulsion layer and a diffusion-resistant α-acylacetanilide yellow coupler, the anilide group of which is substituted by an N-acylsulfamoyl group which is dissolved in a specific organic solvent.
Es ist bekannt, farbige fotografische Bilder durch chromogene Entwicklung herzustellen, d.h. dadurch, daß man bildmäßig belichtete Silberhalogenidemulsionsschichten in Gegenwart geeigneter Farbkuppler mittels geeigneter farbbildender Entwicklersubstanzen - sogenannter Farbentwickler - entwickelt, wobei das in Übereinstimmung mit dem Silberbild entstehende Oxidationsprodukt der Entwicklersubstanzen mit dem Farbkuppler unter Bildung eines Farbstoffbildes reagiert. Als Farbentwickler werden gewöhnlich aromatische, primäre Aminogruppen enthaltende Verbindungen, insbesondere solche vom p-Phenylendiamintyp, verwendet.It is known to produce colored photographic images by chromogenic development, that is to say by developing imagewise exposed silver halide emulsion layers in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called color developers - the oxidation product of the developer substances with the color coupler which is formed in accordance with the silver image being formed of a dye image reacts. Aromatic compounds containing primary amino groups, in particular those of the p-phenylenediamine type, are usually used as color developers.
An die Farbkuppler, sowie an die daraus durch chromogene Entwicklung erhaltenen Farbstoffe werden in der Praxis eine Reihe von Forderungen gestellt. So soll die Kupplungsgeschwindigkeit der Farbkuppler mit dem Oxidationsprodukt des Farbentwicklers möglichst groß sein und es soll eine möglichst hohe maximale Farbdichte erzielt werden können. Die Farbkuppler sowie die daraus erhaltenen Farbstoffe müssen hinreichend stabil sein gegenüber Licht, erhöhter Temperatur und Feuchtigkeit. Dies gilt sowohl für frisches Material, als auch für verarbeitetes Material. Beispielsweise darf der in den Bildweißen des verarbeiteten Materials noch vorhandene restliche Kuppler nicht vergilben. Außerdem sollten die Farbstoffe hinreichend beständig sein gegenüber gasförmigen reduzierenden oder oxidierenden Agentien. Sie müssen ferner diffusionsfest in der Bildschicht verankert sein und sollen sich bei der chromogenen Entwicklung als möglichst feines Korn abscheiden. Schließlich müssen die aus den Farbkupplern bei der chromogenen Entwicklung entstehenden Farbstoffe eine günstige Absorptionskurve aufweisen mit einem Maximum, das der Farbe des jeweils gewünschten Teilbildes entspricht, und möglichst geringen Nebenabsorptionen.In practice, a number of requirements are placed on the color couplers and on the dyes obtained therefrom by chromogenic development. For example, the coupling speed of the color couplers with the oxidation product of the color developer should be as high as possible and the highest possible color density should be achieved. The color couplers and the dyes obtained from them must be sufficiently stable to light, elevated temperature and moisture. This applies to both fresh material and processed material. For example, the remaining coupler still present in the image whites of the processed material must not turn yellow. In addition, the dyes should be sufficiently resistant to gaseous reducing or oxidizing agents. They must also be firmly anchored in the image layer and should separate as fine a grain as possible during the chromogenic development. Finally, the dyes resulting from the color couplers in the chromogenic development must have a favorable absorption curve with a maximum that corresponds to the color of the desired partial image and the lowest possible secondary absorptions.
In besonderem Maße gelten die genannten Forderungen für Gelbkuppler, weil diese in farbfotografischen Aufzeichnungsmaterialien vielfach in der obersten farberzeugenden Schicht angeordnet sind und damit nicht nur besonders stark den Umwelteinflüssen ausgesetzt sind, sondern auch die darunterliegenden Schichten insbesondere hinsichtlich der Schärfe beeinflussen. Es sind daher alle Maßnahmen von Vorteil, durch die die Schichtbelastung besonders der gelbkupplerhaltigen Schicht reduziert werden kann. Aus diesem Grund ist die Verwendung von 2-Äquivalent-Gelbkupplern besonders vorteilhaft.The above-mentioned requirements apply to yellow couplers in particular, because they are often arranged in color photographic recording materials in the uppermost color-generating layer and are therefore not only particularly exposed to environmental influences, but also influence the layers below, particularly with regard to their sharpness. There are Therefore, all measures are advantageous by means of which the layer load, particularly of the layer containing yellow coupler, can be reduced. For this reason, the use of 2-equivalent yellow couplers is particularly advantageous.
Unter den bekannten Gelbkupplern sind insbesondere Verbindungen der Formel (I)
worin
- Y
- einen aliphatischen oder cycloaliphatischen Rest,
- X
- ein Wasserstoffatom oder eine bei Farbkupplung abspaltbare Gruppe,
- R¹
- einen Alkylrest mit 1 bis 20 C-Atomen,
- R²
- einen Alkylrest mit 1 bis 20 C-Atomen,
bedeuten, wobei die Alkylreste R¹ und R² zusammen wenigstens 12 C-Atome aufweisen, vorteilhaft, weil sie große Empfindlichkeit, dark-fading-Stabilität und Tropenstabilität zeigen und in benzylalkoholfreier Entwicklung eine steile Gradation neben großer Farbdichte erzeugen.Known yellow couplers include, in particular, compounds of the formula (I)
wherein
- Y
- an aliphatic or cycloaliphatic radical,
- X
- a hydrogen atom or a group which can be split off on color coupling,
- R¹
- an alkyl radical with 1 to 20 carbon atoms,
- R²
- an alkyl radical with 1 to 20 carbon atoms,
mean, wherein the alkyl radicals R¹ and R² together have at least 12 carbon atoms, advantageous because they show great sensitivity, dark fading stability and tropical stability and produce a steep gradation in addition to high color density in benzyl alcohol-free development.
Ein durch Y dargestellter aliphatischer Rest ist bevorzugt ein tert.-Alkylrest, insbesondere tert.-Butyl. Ein durch Y dargestellter cycloaliphatischer Rest ist beispielsweise ein Cyclohexyl-, Norbornyl- oder Adamantylrest.An aliphatic radical represented by Y is preferably a tert-alkyl radical, in particular tert-butyl. A cycloaliphatic radical represented by Y is, for example, a cyclohexyl, norbornyl or adamantyl radical.
Eine durch X dargestellte bei Farbkupplung abspaltbare Gruppe ist bevorzugt eine über ein Sauerstoffatom oder über ein Stickstoffatom, insbesondere ein Ringstickstoffatom angeknüpfte cyclische Gruppe, z.B. ein über ein Ringstickstoffatom angeknüpfter, gegebenenfalls substituierter 5- oder 6-gliedriger heterocyclischer Ring. Solche auch als Fluchtgruppen bezeichnete abspaltbare Gruppen verleihen üblicherweise dem Kuppler das Verhalten eines 2-Äquivalentkupplers, d.h. der Kuppler benötigt zur Farbkupplung nur halbsoviel entwickelbares Silberhalogenid, wie der entsprechende 4-Äquivalentkuppler, bei dem X ein Wasserstoffatom bedeutet. Zu den Fluchtgruppen zählen auch solche, die fotografisch wirksam sind und beispielsweise die Entwicklung hemmen oder beschleunigen.A group represented by X on color coupling is preferably a cyclic group linked via an oxygen atom or via a nitrogen atom, in particular a ring nitrogen atom, e.g. an optionally substituted 5- or 6-membered heterocyclic ring linked via a ring nitrogen atom. Such cleavable groups, also referred to as escape groups, usually give the coupler the behavior of a 2-equivalent coupler, i.e. the coupler only requires half as much developable silver halide for color coupling as the corresponding 4-equivalent coupler, in which X denotes a hydrogen atom. The refugee groups also include those that are photographically effective and, for example, inhibit or accelerate development.
Die Kuppler sind aus US-A-4 617 256 bekannt.The couplers are known from US-A-4 617 256.
Bevorzugte Kuppler entsprechen der Formel
worin
- R³
- C₁₁-C₂₀-Alkyl,
- R⁴
- C₁-C₄-Alkyl und
- R⁵
- ein gegebenenfalls durch Halogen oder C₁-C₄-Alkyl substituiertes Phenyl bedeuten.
wherein
- R³
- C₁₁-C₂₀ alkyl,
- R⁴
- C₁-C₄ alkyl and
- R⁵
- is a phenyl optionally substituted by halogen or C₁-C₄-alkyl.
Als Beispiele dieser Gelbkuppler seien die folgenden Verbindungen genannt:
Die Kuppler der Formel (I) zeigen den Nachteil, daß die mit den üblichen Farbentwicklern der p-Phenylendiaminreihe aus ihnen erzeugten Farbstoffe unbefriedigende Lichtechtheiten aufweisen. Außerdem sind diese Kuppler in gebräuchlichen Lösungsmitteln wie Trikresylphosphat schwerlöslich, was zu kristallinen Ausscheidungen und somit zu Gießfehlern (sogenannte Punktfehler) führt.The following compounds are mentioned as examples of these yellow couplers:
The couplers of the formula (I) have the disadvantage that the dyes produced from them with the customary color developers of the p-phenylenediamine series have unsatisfactory lightfastness. In addition, these couplers are sparingly soluble in common solvents such as tricresyl phosphate, which leads to crystalline precipitations and thus to casting errors (so-called point errors).
Aufgabe der Erfindung war daher, diese Nachteile zu beheben, ohne daß die positiven Eigenschaften dieser Kupplerklasse verloren gehen.The object of the invention was therefore to remedy these disadvantages without the positive properties of this coupler class being lost.
Es wurde nun überraschend gefunden, daß diese Aufgabe durch die Wahl eines bestimmten Kupplerlösungsmittels ("Ölbildner"), gelöst werden kann.It has now surprisingly been found that this object can be achieved by choosing a particular coupler solvent ("oil former").
Gegenstand der Erfindung ist daher ein farbfotografisches Aufzeichnungsmaterial mit mindestens einer Silberhalogenidemulsionsschicht und einem diffusionsfesten Kuppler der Formel (I), dadurch gekennzeichnet, daß als Ölbildner für die Farbkuppler der Formel (I) flüssige estergruppenhaltige Verbindungen eingesetzt werden, die ein Molekulargewicht von wenigstens 350 aufweisen.The invention therefore relates to a color photographic recording material having at least one silver halide emulsion layer and a diffusion-resistant coupler of the formula (I), characterized in that liquid ester-containing compounds which have a molecular weight of at least 350 are used as oil formers for the color couplers of the formula (I).
Vorzugsweise handelt es sich bei den Ölbildnern um Mono- oder Diester aus aliphatischen oder aromatischen Dicarbonsäuren und aliphatischen oder araliphatischen Alkoholen oder um Polyester aus aliphatischen oder aromatischen Dicarbonsäuren und aliphatischen Diolen.The oil formers are preferably mono- or diesters of aliphatic or aromatic dicarboxylic acids and aliphatic or araliphatic alcohols or polyesters of aliphatic or aromatic dicarboxylic acids and aliphatic diols.
Das Molekulargewicht ist an sich nach oben unbegrenzt, solange die estergruppenhaltigen Verbindungen flüssig sind. Vorzugsweise übersteigt das Molekuargewicht den Wert 1200 nicht.There is no upper limit on the molecular weight as long as the compounds containing ester groups are liquid. The molecular weight preferably does not exceed 1200.
Geeignete Ölbildner sind z.B. Dinonyladipat, Dinonylphthalat, Octadecylenbernsteinsäuremonobenzylester und Polymere aus Adipinsäure oder Phthalsäure und Diolen, z.B. Butandiol und/oder Pentandiol. Bis zu 30 Gew.-% des Ölbidners können durch andere Ölbildner, z.B. Trikresylphosphat oder Polyalkylenglykole ersetzt sein. Vorzugsweise werden die Gelbkuppler aber nur in dem erfindungsgemäßen Ölbildner gelöst.Suitable oil formers are, for example, dinonyl adipate, dinonyl phthalate, octadecylene succinic acid monobenzyl ester and polymers of adipic acid or phthalic acid and diols, for example butanediol and / or pentanediol. Up to 30% by weight of the oil binder can be replaced by other oil formers, for example tricresyl phosphate or polyalkylene glycols. Preferably the yellow couplers are only released in the oil former according to the invention.
Bei der Herstellung des lichtempfindlichen farbfotografischen Aufzeichnungsmaterials werden die diffusionsfesten Gelbkuppler der vorliegenden Erfindung gelöst in den erfindungsgemäßen Ölbildnern gegebenenfalls in Anwesenheit eines Netz- oder Dispergiermittels in bekannter Weise in die Gießlösung der Silberhalogenidemulsionsschichten oder anderer Kolloidschichten eingearbeitet. Die hydrophile Gießlösung kann selbstverständlich neben dem Bindemittel andere übliche Zusätze enthalten. Die Lösung des Farbkupplers braucht nicht direkt in die Gießlösung für die Silberhalogenidemulsionsschicht oder eine andere wasserdurchlässige Schicht dispergiert zu werden; sie kann vielmehr auch vorteilhaft zuerst in einer wäßrigen nicht-lichtempfindlichen Lösung eines hydrophilen Kolloids dispergiert werden, worauf das erhaltene Gemisch mit der Gießlösung für die lichtempfindliche Silberhalogenidemulsionsschicht oder einer anderen wasserdurchlässigen Schicht vor dem Auftragen vermischt wird.In the production of the light-sensitive color photographic recording material, the diffusion-resistant yellow couplers of the present invention are incorporated into the casting solution of the silver halide emulsion layers or other colloid layers in the oil formers according to the invention, if appropriate in the presence of a wetting or dispersing agent. The hydrophilic casting solution can of course contain other conventional additives in addition to the binder. The color coupler solution does not need to be directly dispersed in the casting solution for the silver halide emulsion layer or other water permeable layer; Rather, it can also be advantageously first dispersed in an aqueous non-photosensitive solution of a hydrophilic colloid, whereupon the mixture obtained is mixed with the coating solution for the photosensitive silver halide emulsion layer or another water-permeable layer before application.
Als lichtempfindliche Silberhalogenidemulsionen eignen sich Emulsionen von Silberchlorid, Silberbromid oder Gemische davon, evtl. mit einem geringen Gehalt an Silberiodid bis zu 10 Mol-% in einem der üblicherweise verwendeten hydrophilen Bindemittel. Als Bindemittel für die fotografischen Schichten wird vorzugsweise Gelatine verwendet. Diese kann jedoch ganz oder teilweise durch andere natürliche oder synthetische Bindemittel ersetzt werden.Suitable light-sensitive silver halide emulsions are emulsions of silver chloride, silver bromide or mixtures thereof, possibly with a low silver iodide content of up to 10 mol% in one of the commonly used hydrophilic binders. Gelatin is preferably used as the binder for the photographic layers used. However, this can be replaced in whole or in part by other natural or synthetic binders.
Die erfindungsgemäßen Vorteile werden besonders deutlich, wenn das erfindungsgemäße Colormaterial in den lichtempfindlichen Schichten nur Silberhalogenidemulsion mit mindestens 95 Mol-% Silberchlorid enthält.The advantages according to the invention become particularly clear when the color material according to the invention contains only silver halide emulsion with at least 95 mol% silver chloride in the light-sensitive layers.
Die Emulsionen können in der üblichen Weise chemisch und spektral sensibilisiert sein.The emulsions can be chemically and spectrally sensitized in the usual way.
Die lichtempfindliche Schicht, der der erfindungsgemäße Gelbkuppler zugeordnet ist, ist insbesondere blausensibilisiert.The light-sensitive layer to which the yellow coupler according to the invention is assigned is in particular blue-sensitized.
Das farbfotografische Material, das vorzugsweise einen reflektierenden Träger enthält, enthält außerdem wenigstens eine grünempfindliche Schicht, der ein Purpurkuppler zugeordnet ist und wenigstens eine rotempfindliche Schicht, der ein Blaugrünkuppler zugeordnet ist sowie gegebenenfalls Zwischen- und Schutzschichten.The color photographic material, which preferably contains a reflective support, also contains at least one green-sensitive layer to which a magenta coupler is assigned and at least one red-sensitive layer to which a cyan coupler is assigned, and optionally intermediate and protective layers.
Eine Übersicht über die als Spektralsensibilisatoren geeigneten Polymethinfarbstoffe, deren geeignete Kombinationen und supersensibilisierend wirkenden Kombinationen enthält Research Disclosure 17643/1978 in Abteilung IV.Research Disclosure 17643/1978 in Department IV contains an overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and combinations with a super-sensitizing effect.
Insbesondere sind die folgenden Farbstoffe - geordnet nach Spektralgebieten - geeignet:
- 1. als Rotsensibilisatoren
9-Ethylcarbocyanine mit Benzthiazol, Benzselenazol oder Naphthothiazol als basische Endgruppen, die in 5- und/oder 6-Stellung durch Halogen, Methyl, Methoxy, Carbalkoxy, Aryl substituiert sein können sowie 9-Ethyl-naphthoxathia- bzw. -selencarbocyanine und 9-Ethyl-naphthothiaoxa- bzw. -benzimidazocarbocyanine, vorausgesetzt, daß die Farbstoffe mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff tragen. - 2. als Grünsensibilisatoren
9-Ethylcarbocyanine mit Benzoxazol, Naphthoxazol oder einem Benzoxazol und einem Benzthiazol als basische Endgruppen sowie Benzimidazocarbocyanine, die ebenfalls weiter substituiert sein können und ebenfalls mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff enthalten müssen. - 3. als Blausensibilisatoren
symmetrische oder asymmetrische Benzimidazo-, Oxa-, Thia- oder Selenacyanine mit mindestens einer Sulfoalkylgruppe am heterocyclischen Stickstoff und gegebenenfalls weiteren Substituenten am aromatischen Kern, sowie Apomerocyanine mit einer Rhodaningruppe.
- 1. as red sensitizers
9-ethyl carbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl, and 9-ethyl-naphthoxathia or -selencarbocyanines and 9- Ethyl-naphthothiaoxa- or -benzimidazocarbocyanine, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen. - 2. as green sensitizers
9-ethyl carbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzthiazole as basic end groups, and also benzimidazocarbocyanines, which may also be further substituted and must likewise contain at least one sulfoalkyl group on the heterocyclic nitrogen. - 3. as blue sensitizers
symmetrical or asymmetrical benzimidazo, oxa, thia or selenacyanines with at least one sulfoalkyl group on the heterocyclic nitrogen and optionally further substituents on the aromatic nucleus, and apomerocyanines with a rhodanine group.
Bei den Farbkupplern kann es sich um 4-Äquivalentkuppler, aber auch um 2-Äquivalentkuppler handeln. Letztere leiten sich von den 4-Äquivalentkupplern dadurch ab, daß sie in der Kupplungsstelle einen Substituenten enthalten, der bei der Kupplung abgespalten wird. Zu den 2-Äquivalentkupplern sind solche zu rechnen, die farblos sind, als auch solche, die eine intensive Eigenfarbe aufweisen, die bei der Farbkupplung verschwindet bzw. durch die Farbe des erzeugten Bildfarbstoffes ersetzt wird (Maskenkuppler), und die Weißkuppler, die bei Reaktion mit Farbentwickleroxidationsprodukten im wesentlichen farblose Produkte ergeben. Zu den 2-Äquivalentkupplern sind ferner solche Kuppler zu rechnen, die in der Kupplungsstelle einen abspaltbaren Rest enthalten, der bei Reaktion mit Farbentwickleroxidationsprodukten in Freiheit gesetzt wird und dabei entweder direkt oder nachdem aus dem primär abgespaltenen Rest eine oder mehrere weitere Gruppen abgespalten worden sind (z.B. DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), eine bestimmte erwünschte fotografische Wirksamkeit entfaltet, z.B. als Entwicklungsinhibitor oder -accelerator. Beispiele für solche 2-Äquivalentkuppler sind die bekannten DIR-Kuppler wie auch DAR-bzw. FAR-Kuppler.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 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products. The 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue ( e.g. DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, e.g. as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
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 coupler for generating the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type.
Die Einarbeitung der Blaugrün- und Purpurkuppler kann in der gleichen Weise und mit den gleichen Ölbildnern wie bei den Gelbkupplern erfolgen.The blue-green and purple couplers can be incorporated in the same way and with the same oil formers as the yellow couplers.
Geeignete Ölbildner für Purpur- und Blaugrünkuppler sind zusätzlich andere Phthalsäurealkylester, Phosphonsäureester, Phosphorsäureester, Citronensäureester, Benzoesäureester, Amide, Fettsäureester, Trimesinsäureester, Alkohole, Phenole, Anilinderivate und Kohlenwasserstoffe.Suitable oil formers for magenta and cyan couplers are in addition other alkyl phthalates, phosphonic 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.
Die in der Regel zwischen Schichten unterschiedlicher Spektralempfindlichkeit angeordneten nicht lichtempfindlichen Zwischenschichten können Mittel enthalten, die eine unerwünschte Diffusion von Entwickleroxidationsprodukten aus einer lichtempfindlichen in eine andere lichtempfindliche Schicht mit unterschiedlicher spektraler Sensibilisierung verhindern.The non-light-sensitive intermediate layers, which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products prevent from one photosensitive to another photosensitive layer with different spectral sensitization.
Geeignete Mittel, die auch Scavenger oder EOP-Fänger genannt werden, werden in Research Disclosure 17 643 (Dez. 1978), Kapitel VII, 17 842/1979, Seite 94-97 und 18.716/ 1979, Seite 650 sowie in EP-A-69 070, 98 072, 124 877, 125 522 und in US-A-463 226 beschrieben.Suitable agents, which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), Chapter VII, 17 842/1979, pages 94-97 and 18.716 / 1979, page 650 and in EP-A- 69,070, 98,072, 124,877, 125,522 and in US-A-463,226.
Bei dem als lichtempfindlicher Bestandteil in dem fotografischen Material befindliche Silberhalogenid kann es sich um überwiegend kompakte Kristalle handeln, die z.B. regulär kubisch oder oktaedrisch sind oder Übergangsformen aufweisen können. Vorzugsweise können aber auch 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 wesentlich größer als 5:1 ist, z.B. 12:1 bis 30:1.The silver halide present as a light-sensitive component in the photographic material can be predominantly compact crystals, which are e.g. are regular cubic or octahedral or can have transitional forms. However, platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being 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 substantially greater than 5: 1, e.g. 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. Homodisperse Korngrößenverteilung bedeutet, daß 95 % der Körner nicht mehr als ± 30% von der mittleren Korngröße abweichen. Die Emulsionen können neben 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 doping of the individual grain areas, being different. The middle The 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. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ± 30%. In addition to the silver halide, the emulsions can also contain organic silver salts, for example 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.
Während der Fällung und/oder der physikalischen Reifung der Silberhalogenidkörner können auch Salze oder Komplexe von Metallen, wie Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe vorhanden sein.Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe can also be present during the precipitation and / or physical ripening of the silver halide grains.
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, for example by changing the pH or by an oxidative treatment.
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 Silberhalogenidemulsion wird im allgemeinen einer chemischen Sensibilisierung unter definierten Bedingungen - pH, pAg, Temperatur, Gelatine-, Silberhalogenid-und Sensibilisatorkonzentration - bis zum Erreichen des Empfindlichkeits- und Schleieroptimums unterworfen. Die Verfahrensweise ist z.B. bei H. Frieser "Die Grundlagen der Photographischen Prozesse mit Silberhalogeniden" Seite 675-734, Akademische Verlagsgesellschaft (1968) beschrieben.The silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog have been reached. The procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).
Dabei kann die chemische Sensibilisierung unter Zusatz von Verbindungen von Schwefel, Selen, Tellur und/oder Verbindungen der Metalle der VIII. Nebengruppe des Periodensystems (z.B. Gold, Platin, Palladium, Iridium) erfolgen, weiterhin können Thiocyanatverbindungen, oberflächenaktive Verbindungen, wie Thioether, heterocyclische Stickstoffverbindungen (z.B. Imidazole, Azaindene) oder auch spektrale Sensibilisatoren (beschrieben z.B. bei F. Hamer "The Cyanine Dyes and Related Compounds", 1964, bzw. Ullmanns Encyclopädie der technischen Chemie, 4. Auflage, Bd. 18, S. 431 ff. und Research Disclosure Nr. 17643, Abschnitt III) zugegeben werden. Ersatzweise oder zusätzlich kann eine Reduktionssensibilisierung unter Zugabe von Reduktionsmitteln (Zinn-II-Salze, Amine, Hydrazinderivate, Aminoborane, Silane, Formamidinsulfinsäure) durch Wasserstoff, durch niedrigen pAg (z.B. kleiner 5) und/oder hohen pH (z.B. über 8) durchgeführt werden.Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (for example gold, platinum, palladium, iridium). Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic compounds can also be used Nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia of Industrial Chemistry, 4th edition, vol. 18, pp. 431 ff. and Research Disclosure No. 17643, Section III). As an alternative or in addition, reduction sensitization with the addition of reducing agents (tin-II salts, Amines, hydrazine derivatives, aminoboranes, silanes, formamidinesulfinic acid) can be carried out by hydrogen, by low pAg (for example less than 5) and / or high pH (for example above 8).
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, gegebenenfalls substituierte Benztriazole oder Benzthiazoliumsalze eingesetzt werden. Besonders 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 for example from 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 such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can also be used as antifoggants. Heterocycles containing mercapto groups, for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain 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 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.). Neben natürlichen oberflächenaktiven Verbindungen, z.B. Saponin, finden hauptsächlich synthetische oberflächenaktive Verbindungen (Tenside) Verwendung: nicht-ionische Tenside, z.B. Alkylenoxidverbindungen, Glycerinverbindungen oder Glycidolverbindungen, kationische Tenside, z.B. höhere Alkylamine, quartäre Ammoniumsalze, Pyridinverbindungen und andere heterocyclische Verbindungen, Sulfoniumverbindungen oder Phosphoniumverbindungen, anionische Tenside, enthaltend eine Säuregruppe, z.B. Carbonsäure-, Sulfonsäure-, eine Phosphorsäure-, Schwefelsäureester- oder Phosphorsäureestergruppe, ampholytische Tenside, z.B. Aminosäure- und Aminosulfonsäureverbindungen sowie Schwefel- oder Phosphorsäureester eines Aminoalkohols.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 ( eg acceleration of development, high contrast, sensitization etc.). In addition to natural surface-active compounds, for example saponin, synthetic surface-active compounds (surfactants) are mainly used: non-ionic surfactants, for example alkylene oxide compounds, glycerol compounds or glycidol compounds, cationic surfactants, for example higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, for example carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, for example amino acid and aminosulfonic acid compounds and sulfur or phosphoric acid esters of an amino alcohol.
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).
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 binder layers, in particular the layer furthest away from the carrier, but also occasionally intermediate layers, especially if they represent the layer furthest away from the carrier during production, can contain photographically inert particles of an inorganic or organic nature, e.g. 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.
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-dichlor-1,3,5-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-3 017 280 und US-A-2 983 611); Säurederivate (US-A-2 725 294 und US-A-2 725 295); Verbindungen vom Carbodiimidtyp (US-A-3 100 704); Carbamoylpyridiniumsalze (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 are, for example, 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, the reactive halogen included (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-3 017 280 and US-A-2 983 611); Acid derivatives (US-A-2 725 294 and US-A-2 725 295); Carbodiimide type compounds (US-A-3 100 704); Carbamoylpyridinium 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 with 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 the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry caused by the crosslinking reaction 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.
Farbfotografische Negativmaterialien werden üblicherweise durch Entwickeln, Bleichen, Fixieren und Wässern oder durch Entwickeln, Bleichen, Fixieren und Stabilisieren ohne nachfolgende Wässerung verarbeitet, wobei Bleichen und Fixieren zu einem Verarbeitungsschritt zusammengefaßt sein können. Als Farbentwicklerverbindung lassen sich sämtliche Entwicklerverbindungen verwenden, die die Fähigkeit besitzen, in Form ihres Oxidationsproduktes mit Farbkupplern zu Azomethin- bzw. Indophenolfarbstoffen zu reagieren. Geeignete Farbentwicklerverbindungen sind aromatische, mindestens eine primäre Aminogruppe enthaltende Verbindungen vom p-Phenylendiamintyp, beispielsweise N,N-Dialkyl-p-phenylendiamine wie N,N-Diethyl-p-phenylendiamin, 1-(N-Ethyl-N-methansulfonamidoethyl)-3-methyl-p-phenylendiamin, 1-(N-Ethyl-N-hydroxyethyl)-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.Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step. 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-phenylenediamine 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-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine. 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.
Nach der Farbentwicklung kann ein saures Stoppbad oder eine Wässerung folgen.After the color development, an acidic stop bath or watering can follow.
Üblicherweise wird das Material unmittelbar nach der Farbentwicklung gebleicht und fixiert. Als Bleichmittel können z.B. Fe(III)-Salze und Fe(III)-Komplexsalze wie Ferricyanide, Dichromate, wasserlösliche Kobaltkomplexe verwendet werden. Besonders bevorzugt sind Eisen-(III)-Komplexe von Aminopolycarbonsäuren, insbesondere z.B. von Ethylendiamintetraessigsäure, Propylendiamintetraessigsäure, Diethylentriaminpentaessigsäure, Nitrilotriessigsäure, Iminodiessigsäure, N-Hydroxyethyl-ethylendiamintriessigsäure, Alkyliminodicarbonsäuren und von entsprechenden Phosphonsäuren. Geeignete als Bleichmittel sind weiterhin Persulfate und Peroxide, z.B. Wasserstoffperoxid.Usually the material is bleached and fixed immediately after color development. As bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used. Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulphates and peroxides, e.g. Hydrogen peroxide.
Auf das Bleichfixierbad oder Fixierbad folgt meist eine Wässerung, die als Gegenstromwässerung ausgeführt ist oder aus mehreren Tanks mit eigener Wasserzufuhr besteht.The bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.
Günstige Ergebnisse können bei Verwendung eines darauf folgenden Schlußbades, das keinen oder nur wenig Formaldehyd enthält, erhalten werden.Favorable results can be obtained using a subsequent final bath which contains little or no formaldehyde.
Die Wässerung kann aber durch ein Stabilisierbad vollständig ersetzt werden, das üblicherweise im Gegenstrom geführt wird. Dieses Stabilisierbad übernimmt bei Formaldehydzusatz auch die Funktion eines Schlußbades.However, the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent. When formaldehyde is added, this stabilizing bath also functions as a final bath.
Jeweils 8 mMol der nachstehend aufgeführten Kuppler wurden in 15 ml Essigester, 5 ml des nachstehend angegebenen Ölbildners und 5 ml einer 10 gew.-%igen wäßrigen Lösung des Natriumsalzes einer C₁₂-Alkylnaphthylsulfonsäure gelöst und bei 60°C in 150 ml 7,5 gew.-%iger wäßriger Gelatinelösung emulgiert. Dem fertigen Emulgat wurde 126 ml einer Silberbromidchloridemulsion (99 Mol-% AgCl), mit einem Silbergehalt der 6,8 g AgNO₃ entspricht, zugesetzt. Diese Gießlösung wurde bei 40°C mit einem Auftrag von 1,5 g AgNO₃ pro m² auf ein polyethylenbeschichtetes Papier aufgegossen.In each case 8 mmol of the couplers listed below were dissolved in 15 ml of ethyl acetate, 5 ml of the oil former specified below and 5 ml of a 10% by weight aqueous solution of the sodium salt of a C₁₂-alkylnaphthylsulfonic acid and at 60 ° C in 150 ml of 7.5% .-% emulsified aqueous gelatin solution. The finished emulsate was added 126 ml of a silver bromide chloride emulsion (99 mol% AgCl), with a silver content corresponding to 6.8 g AgNO₃. This casting solution was poured onto a polyethylene-coated paper at 40 ° C. with an order of 1.5 g AgNO₃ per m².
Auf diese Schicht wurde eine Schutzschicht von 0,9 g/m² Gelatine und 0,3 g/m² des Härtungsmittels der Formel
aufgetragen und die Proben getrocknet.A protective layer of 0.9 g / m² of gelatin and 0.3 g / m² of the hardening agent of the formula was applied to this layer
applied and the samples dried.
Die Proben wurden hinter einem Graustufenkeil belichtet, in dem nachstehend angegebenen Farbentwickler entwickelt, anschließend bleichfixiert, gewässert und getrocknet.The samples were exposed behind a grayscale wedge, developed in the color developer specified below, then fixed to bleach, washed and dried.
Die Ergebnisse der sensitometrischen Prüfen sind in Tabelle 1 angegeben.
- DBP =
- Dibutylphthalat
- TKP =
- Trikresylphosphat
- DLA =
- Diethylauramid
- A =
- Diisononylphthalsäureester
- B =
- Polyester aus Adipinsäure und einer Mischung aus 1,3-, 1,4-Butandiol und 2-Ethylpropandiol-1,3
- C =
- Polyester aus Phthalsäure und einer Mischung aus Hexandiol-1,6 und Isodecylalkohol
- D =
- Polyester aus Adipinsäure und einer Mischung aus 1,3-Butylenglykol und 1,6-Hexandiol
- E =
- 1:1-Mischung aus den Ölformen A und B
- F =
- 3:1-Mischung aus Ölformer B und dem Polypropylenglykol der Formel
- DBP =
- Dibutyl phthalate
- CPM =
- Tricresyl phosphate
- DLA =
- Diethylauramide
- A =
- Diisononylphthalic acid ester
- B =
- Polyester from adipic acid and a mixture of 1,3-, 1,4-butanediol and 2-ethylpropanediol-1,3
- C =
- Polyester from phthalic acid and a mixture of 1,6-hexanediol and isodecyl alcohol
- D =
- Polyester made from adipic acid and a mixture of 1,3-butylene glycol and 1,6-hexanediol
- E =
- 1: 1 mixture of oil forms A and B.
- F =
- 3: 1 mixture of oil former B and the polypropylene glycol of the formula
Dmin = Schleier; E₀,₆ = Empfindlichkeit bei Dichte 0,6; G1 = Schwellengradation; G2 = Schultergradation, Dmax = Maximaldichte; Xe = Bestimmung der Lichtechtheit im Xenotest mit 15.10⁶ Lux.h; Df = Darkfadingtest 3 Wochen bei 80°C und 40 % rel. Luftfeuchte; Tr = Tropenlagerung 14 Tage bei 60°C und 90 % relativer Feuchte; ΔD(1,0) = Dichteveränderung bei Dichte 1,0 in %;
Kuppler V1 hat die Formel:
Es zeigt sich, daß bei Verwendung von DBP die Lichtechtheit des gebildeten Farbstoffs schlechter ist als mit erfindungsgemäßen Ölformern, daß bei Verwendung von DLA-Nachteile in der Tropenstabilität auftreten und daß der Vergleichskuppler V1 sogar in erfindungsgemäßen Lösungsmitteln niedrige Empfindlichkeit, schlechte Darkfadingstabilität und schlechte Tropenstabilität zeigt. TKP ist hinsichtlich der sensitometrischen Eigenschaften den erfindungsgemäßen Ölbildner vergleichbar, zeigt aber eine gegenüber den erfindungsgemäßen Proben erhöhte Anzahl von Gießfehlern, was in Beispiel 2 gezeigt wird.D min = veil; E₀ , ₆ = sensitivity at density 0.6; G1 = threshold gradation; G2 = shoulder gradation, D max = maximum density; Xe = determination of the light fastness in the Xenotest with 15.10⁶ lux.h; Df = Darkfading test 3 weeks at 80 ° C and 40% rel. Air humidity; Tr = tropical storage for 14 days at 60 ° C and 90% relative humidity; ΔD (1.0) = density change at density 1.0 in%;
Coupler V1 has the formula:
It turns out that when DBP is used the lightfastness of the dye formed is worse than with oil formers according to the invention, that when using DLA disadvantages in tropical stability occur and that the comparative coupler V1 shows low sensitivity, poor dark fading stability and poor tropical stability even in solvents according to the invention . TKP is comparable to the oil formers according to the invention with regard to the sensitometric properties, but shows an increased number of pouring errors compared to the samples according to the invention, which is shown in Example 2.
Die Proben 4 bis 11 sind erfindungsgemäß.Samples 4 to 11 are according to the invention.
Auf einen Schichtträger aus beidseitig mit Polyethylen beschichtetem Papier wurden die folgenden Schichten in der angegebenen Reihenfolge aufgetragen. Die Mengenangaben beziehen sich jeweils auf 1 m². Für den Silberhalogenidauftrag werden die entsprechenden Mengen AgNO₃ angegeben.
- 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 0,63 g AgNO₃ mit
1,38 g Gelatine
0,95 g Gelbkuppler 15
0,2 g Weißkuppler W-1
0,55 g Ölbildner gemäß Tabelle 2 - 3. Schicht (Schutzschicht)
1,1 g Gelatine
0,06 g 2,5-Dioctylhydrochinon
0,06 g Dibutylphthalat (DBP) - 4. Schicht (grünempfindliche Schicht)
grünsensibilisierte Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,6 µm) aus 0,45 g AgNO₃ mit
1,08 g Gelatine
0,41 g Purpurkuppler M-1
0,08 G 2,5-Dioctylhydrochinon
0,34 g DBP
0,20 g TKP - 5. Schicht (UV-Schutzschicht)
1,15 g Gelatine
0,06 g UV-Absorber der Formel
0,04 g TKP - 6. Schicht (rotempfindliche Schicht)
rotsensibilisierte Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,5 µm) aus 0,3 g AgNO 3 mit
0,75 g Gelatine
0,36 g Blaugrünkuppler C-1
0,36 TKP - 7. Schicht (UV-Schicht)
0,35 g Gelatine
0,15 g UV-Absorber wie Schicht 5
0,2 g TKP - 8. Schicht (Schutzschicht)
0,9 g Gelatine
0,3 g Härtungsmittel der Formel
- 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 µm) from 0.63 g AgNO₃ with
1.38 g gelatin
0.95 g yellow coupler 15
0.2 g white coupler W-1
0.55 g of oil generator according to Table 2 - 3rd layer (protective layer)
1.1 g gelatin
0.06 g 2,5-dioctylhydroquinone
0.06 g dibutyl phthalate (DBP) - 4th layer (green-sensitive layer)
green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.6 µm) from 0.45 g AgNO₃ with
1.08 g gelatin
0.41 g purple coupler M-1
0.08 G 2,5-dioctyl hydroquinone
0.34 g DBP
0.20 g CPM - 5th layer (UV protective layer)
1.15 g gelatin
0.06 g UV absorber of the formula
0.04 g CPM - 6th layer (red-sensitive layer)
red-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 µm) from 0.3 g AgNO 3 with
0.75 g gelatin
0.36 g of cyan coupler C-1
0.36 CPM - 7th layer (UV layer)
0.35 g gelatin
0.15 g UV absorber as layer 5
0.2 g CPM - 8th layer (protective layer)
0.9 g gelatin
0.3 g hardening agent of the formula
Es wurde die Emulgat-Stabilität dadurch geprüft, daß am gegossenen Material punktförmige Gelbkupplerabscheidungen/m² ausgezählt wurden, wobei bei der Herstellung des Materials zum einen eine frisch hergestellte Kupplerlösung ("frisch") und zum anderen eine 24h bei 40°C gelagerte Kupplerlösung ("gelagert") eingesetzt wurden. Die Ergebnisse sind Tabelle 2 zu entnehmen.
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4000844 | 1990-01-13 | ||
DE4000844A DE4000844A1 (en) | 1990-01-13 | 1990-01-13 | COLOR PHOTOGRAPHIC RECORDING MATERIAL |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0437818A2 true EP0437818A2 (en) | 1991-07-24 |
EP0437818A3 EP0437818A3 (en) | 1991-10-09 |
EP0437818B1 EP0437818B1 (en) | 1995-09-06 |
Family
ID=6398026
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90125261A Expired - Lifetime EP0437818B1 (en) | 1990-01-13 | 1990-12-21 | Colour photographic recording material |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0437818B1 (en) |
DE (2) | DE4000844A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0632325A1 (en) * | 1993-07-02 | 1995-01-04 | Agfa-Gevaert AG | Colour photographic material |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5605785A (en) * | 1995-03-28 | 1997-02-25 | Eastman Kodak Company | Annealing processes for nanocrystallization of amorphous dispersions |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3441525A1 (en) * | 1984-11-14 | 1986-05-15 | Agfa-Gevaert Ag, 5090 Leverkusen | COLOR PHOTOGRAPHIC COLOR COUPLING RECORD MATERIAL |
DE3835202A1 (en) * | 1988-10-15 | 1990-04-19 | Agfa Gevaert Ag | COLOR PHOTOGRAPHIC RECORDING MATERIAL |
-
1990
- 1990-01-13 DE DE4000844A patent/DE4000844A1/en not_active Withdrawn
- 1990-12-21 DE DE59009631T patent/DE59009631D1/en not_active Expired - Fee Related
- 1990-12-21 EP EP90125261A patent/EP0437818B1/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3441525A1 (en) * | 1984-11-14 | 1986-05-15 | Agfa-Gevaert Ag, 5090 Leverkusen | COLOR PHOTOGRAPHIC COLOR COUPLING RECORD MATERIAL |
DE3835202A1 (en) * | 1988-10-15 | 1990-04-19 | Agfa Gevaert Ag | COLOR PHOTOGRAPHIC RECORDING MATERIAL |
EP0364807A2 (en) * | 1988-10-15 | 1990-04-25 | Agfa-Gevaert AG | Colour-photographic recording material |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0632325A1 (en) * | 1993-07-02 | 1995-01-04 | Agfa-Gevaert AG | Colour photographic material |
Also Published As
Publication number | Publication date |
---|---|
DE4000844A1 (en) | 1991-07-18 |
DE59009631D1 (en) | 1995-10-12 |
EP0437818A3 (en) | 1991-10-09 |
EP0437818B1 (en) | 1995-09-06 |
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