EP0377181A2 - Matériau photographique couleur - Google Patents

Matériau photographique couleur Download PDF

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Publication number
EP0377181A2
EP0377181A2 EP89123723A EP89123723A EP0377181A2 EP 0377181 A2 EP0377181 A2 EP 0377181A2 EP 89123723 A EP89123723 A EP 89123723A EP 89123723 A EP89123723 A EP 89123723A EP 0377181 A2 EP0377181 A2 EP 0377181A2
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EP
European Patent Office
Prior art keywords
silver halide
color
photosensitive
compounds
layer
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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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EP89123723A
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German (de)
English (en)
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EP0377181A3 (fr
Inventor
Reinhart Dr. Matejec
Erich Dr. Wolff
Heinrich Dr. Odenwälder
Hans Dr. Öhlschläger
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication of EP0377181A3 publication Critical patent/EP0377181A3/fr
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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
    • G03C7/32—Colour coupling substances
    • G03C7/3212—Couplers characterised by a group not in coupling site, e.g. ballast group, as far as the coupling rest is not specific
    • 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

Definitions

  • the invention relates to a light-sensitive, color photographic silver halide material, in particular a color negative material, with an improved sensitivity-graininess ratio.
  • color photographic images by chromogenic development, i.e. 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 which is formed in accordance with the silver image reacting with the color coupler to form a dye image.
  • color developers i.e. 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 which is formed in accordance with the silver image reacting with the color coupler to form a dye image.
  • Aromatic compounds containing primary amino groups in particular those of the p-phenylenediamine type, are usually used as color developers.
  • the sensitivity can be increased by using larger silver halide grains. However, this usually leads to a deterioration in the color grain.
  • the sensitivity can also be increased by so-called development accelerators (e.g. quaternary salts, polyethylene oxides and others; see, for example, TH James, The Theory of the Photographic Process, Mac Millan Co., New York / Londen, 4th ed. (1977) p. 422- 426) can be increased.
  • development accelerators e.g. quaternary salts, polyethylene oxides and others; see, for example, TH James, The Theory of the Photographic Process, Mac Millan Co., New York / Londen, 4th ed. (1977) p. 422- 426) can be increased.
  • a stronger development of the silver halide grains also increases the color granularity; there are also limits to the effect of development accelerators.
  • Sensitivity can also be increased by using compounds that release imaging or development enhancing agents during development.
  • Such compounds are described for example in DE-A-32 09 110, DE-A-33 33 355, EP-A-0 117 511 and EP-A-0 118 087.
  • the disadvantage associated with the use of such compounds is generally due to an intensification of the latent veil, even in the unexposed areas, so that images with an increased basic veil are obtained.
  • a coarser grain of color is also obtained, at least in the area of low color densities.
  • the object of the invention was to improve the sensitivity / granularity ratio of photosensitive, color photographic silver halide materials without the aforementioned disadvantages occurring.
  • the invention therefore relates to a light-sensitive, color-photographic silver halide material with at least one light-sensitive silver halide layer, to which a conventional diffusion-resistant color coupler is assigned, and optionally further light-sensitive and non-light-sensitive layers, characterized in that the at least one light-sensitive silver halide layer in a concentration of 10 ⁇ 3 up to 10 mmol, preferably 10 -2 to 1 mmol / mol silver halide, a compound adhering to the silver halide grain with the developer oxidation product (EOP) with an effective reaction rate constant k eff ⁇ 103, preferably ⁇ 104 1 / mol.s, of the compound A ⁇ Z ⁇ K (I) contains adsorbed on the silver halide grain, in which A is a grain-active adhesive group of the formulas IIa to IId: Z1 the remaining members to complete a preferably 5- or 6-membered ring which contains at least one further heteroatom such as a nitrogen or sulfur atom and is optionally benzo-
  • Preferred divalent intermediate members Z are alkylene groups, arylene groups, -COCH2-, -COCH2-S-, -COCH2-O-, Suitable adhesive groups IIa and IIb are derived from the following heterocycles:
  • Imidazole benzotriazole, 1,2,3-triazole, 1,2,4-triazole, benztriazole, tri-, tetra- and pentaazaindene, such as 1,3,3a, 7-tetraazaindene and 1,2,3,3a, 7 -Pentaazaindene, oxazole, thiazole, selenazole, oxadiazole, thiadiazole, tetrazole, pyridine and pyrimidine.
  • heterocycles can optionally be substituted, in particular by alkyl, aryl, nitro, amino, hydroxy, carboxy, sulfo, halogen, cyano, alkylsulfonyl, alkyl- or arylthio, which in turn can be further substituted.
  • Alkyl is in particular C1-C4 alkyl; Aryl especially phenyl.
  • Coupling part K is to be understood as meaning those compounds which, owing to an active coupling point in the molecule, are able to react with the oxidation product of a color developer (e.g. p-phenylenediamine derivatives). These include the large class of color couplers (see Pelz: Announcements from the research laboratories of Agfa Volume III p.
  • 111 ff for example: yellow couplers of the ⁇ -ketocarboxylic acid type, purple couplers of the anilinopyrazolone type, acylaminopyrazolones, cyanacetophenone, pyrazoloazole magenta couplers, Pyrazolobenzimidazoles, phenolic and naphtholic teal couplers and couplers that form colorless coupling products.
  • the coupling point can be unsubstituted or carry a substituent that is split off during the coupling (escape group), for example Cl ⁇ or Br ⁇ , and the usual split-off groups of 2-equivalent couplers.
  • the split-off group can in turn be photographically effective, like the split-off groups in the known DIR, DAR and FAR couplers.
  • the coupling residues can also be the remains of so-called white couplers.
  • the coupling residues can themselves be colored and deliver colorless or differently colored products during the coupling (mask coupler).
  • the compounds of the formula I according to the invention generally have no diffusion-inhibiting ballast groups, as are known from conventional color couplers.
  • the compounds of the formula I can be dissolved in customary solvents, for example in the form of aqueous, aqueous-alkaline or aqueous-alcoholic solutions, and added to the casting solutions. They are preferably added to the silver halide emulsions before the addition of couplers.
  • detention groups A are:
  • the measuring apparatus shown in Fig. 1 consists of the cylindrical approximately 25 cm high storage containers 1 and 2, the supply lines 3 equipped with check valves, the mixing chamber 4, the solenoid valve 5, which is closed in the idle state and can be opened via the pulse generator 6, the Collecting vessel 7, in which a negative pressure is generated and maintained, the measuring electrode 8a, the reference electrode 8b, the digital mV meter 9 and the recorder 10.
  • the solenoid valve 5 is opened for a time t by means of the pulse generator 6.
  • the liquids contained in the latter flow via the feed lines 3 into the mixing chamber, where intensive mixing takes place.
  • the mixture then passes through the solenoid valve 5 into the collecting vessel 7.
  • Storage container 1 contains an oxidizing agent, for example a 10 ⁇ 3 molar aqueous solution of K3 [Fe (CN) 6].
  • Storage container 2 contains a color developer, the substance to be examined and means for setting a desired pH value (buffer), all in an aqueous solution.
  • 2-methyl-N-ethyl-hydroxyethyl-p-phenylenediamine was used in particular (concentration: 2x10 ⁇ 3 mol).
  • concentration of the substance to be measured was 10 ⁇ 3 mol.
  • a pH of 10.2 was set using a carbonate / hydrogen carbonate buffer.
  • the redox potential in the mixture is measured with the measuring electrode 8a (platinum wire ⁇ 1 mm);
  • An Ag / AgCl electrode (e.g. Argenthal cartridge) serves as the reference electrode 8b, which in this embodiment is located in the supply line of the storage container 2 to the mixing chamber, but can also be attached as usual next to the platinum electrode.
  • the measured redox potential of the mixed solutions can be read with the aid of the digital mV meter 9 and the chronological course can be recorded by means of the recorder 10 (compensation recorder, oscillograph, light-point line recorder).
  • the time course of the change in the redox potential is shown in FIG. 2.
  • the measured redox potential is plotted in mV (ordinate) as a function of time in sec (abscissa).
  • t represents the opening time of the solenoid valve.
  • the effective reaction rate constant k eff can be calculated from the angle ⁇ using the following equation: wherein k eff is the reaction rate constant [l / mol.s], c o the initial concentration of the substance to be measured [mol / l], f the electrochemical constant [RT / nF], ⁇ K the angle ⁇ obtained when the substance to be determined is present, and ⁇ o the angle ⁇ obtained if the substance to be determined is not present.
  • the mixing chamber 4 and the supply and discharge lines are rinsed vigorously by opening the solenoid valve 5 for a longer time and the containers are then refilled to the original level.
  • the potential-time curve shown in FIG. 2 can then be recorded by briefly opening the solenoid valve 5.
  • the angle ⁇ (FIG. 2) between the time axis and the tangent to the measurement curve at the beginning of the reaction is determined, once with the substance to be measured ( ⁇ K ) and once again without substance ( ⁇ o ).
  • the effective reaction rate constant k eff can be determined by inserting the two ⁇ values in the above equation.
  • the compounds according to the invention are preferably diffusible and are therefore not firmly embedded in the intermediate phase between the halogen silver grains.
  • Water-soluble compounds or those which are soluble in water-miscible organic solvents such as methanol or acetone are therefore preferable.
  • the amounts in which the substances according to the invention are used are in particular 10 ⁇ 3 to 10 mmol, preferably 10 ⁇ 2 to 1 mmol / mol silver halide.
  • the photographic sensitivity initially increases with increasing amounts and then decreases again.
  • the optimal amount within the specified range can easily be determined by simple tests.
  • the diffusion-resistant color coupler that is also present in the layer and provides the image dye there is usually present in a substantially larger amount than the compounds according to the invention, and since the reaction products of the compounds according to the invention with the developer oxidation product generally disappear from the layer during processing, the color which these reaction products have plays only a minor role.
  • the reaction product can be colorless, yellow, purple, blue-green, blue, green, red or have any other color.
  • color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the silver color bleaching process.
  • Suitable supports for the production of color photographic materials are e.g. Films and sheets of semi-synthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or ⁇ -olefin polymer layer (e.g. polyethylene).
  • These supports can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light.
  • the surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.
  • the color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.
  • Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.
  • 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-vinylpyrrolidone, 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, polysaccharides, starch or alginates.
  • Semi-synthetic gelatin substitutes are usually modified natural products.
  • cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers.
  • 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. Oxidized gelatin can also be used. The production such gelatins are described, for example, in The Science and Technology of Gelatine, edited by AG 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 silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide.
  • the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide.
  • silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions with a high chloride content are used up to pure silver chloride emulsions.
  • the crystals can be predominantly compact, which are, for example, regularly 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, where the ratio of diameter to thickness is significantly 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 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. 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, 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, a fine-grained, so-called Lippmann emulsion preferably being mixed with a less soluble emulsion and being redissolved on the latter.
  • 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, e.g. 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 are reached.
  • the procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).
  • a reduction sensitization with the addition of reducing agents can be carried out by hydrogen, by low pAg (eg less than 5) and / or high pH (eg 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 can also be used as antifoggants such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzthiazolium salts.
  • metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles
  • antifoggants such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzthiazolium salts.
  • 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.).
  • 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.).
  • coating aids to prevent electrical charging
  • to improve the sliding properties to emulsify the dispersion
  • adhesion eg 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
  • 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 emulsions can be spectrally sensitized using methine dyes or other dyes.
  • Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • 9-ethylcarbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups the can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl and 9-ethyl-naphthoxathia or -selenecarbocyanine and 9-ethyl-naphthothiaoxa- or -benzimidazocarbocyanine, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.
  • Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromides.
  • 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.
  • the red-sensitive layers usually turn blue green couplers, the green-sensitive layers of purple couplers and the blue-sensitive layers of yellow couplers.
  • Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; suitable examples are
  • 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 of this are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers of the formulas
  • 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 point, 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 (eg DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolds, for example as a development inhibitor or accelerator.
  • Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
  • white couplers are:
  • DIR couplers which release development inhibitors of the azole type, for example triazoles and benzotriazoles, are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 27 26 180, 36 26 219, 36 30 564, 36 36 824, 36 44 416 and 28 42 063. Further advantages for color reproduction, that is, color separation and color purity, and for detail reproduction, that is, sharpness and granularity, can be achieved with those DIR couplers which, for example, do not split off the development inhibitor directly as a result of coupling with an oxidized color developer, but only after a further follow-up reaction, which is achieved, for example, with a timing group.
  • DIR couplers which release a development inhibitor which is decomposed into essentially photographically ineffective products in the developer bath are described, for example, in DE-A-32 09 486 and in EP-A-167 168 and 219 713. This measure ensures trouble-free development and processing consistency.
  • the DIR couplers can be added to a wide variety of layers in a multilayer photographic material, for example also light-insensitive or intermediate layers. However, they are preferably added to the light-sensitive silver halide emulsion layers, the characteristic properties of the silver halide emulsion, for example its iodide content, the structure of the silver halide grains or their grain size distribution having an influence on the photographic properties achieved.
  • the influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it may be advantageous to insert a DIR coupler set, which forms in the respective layer in which it is introduced, a color different from the color to be generated in this layer in the coupling.
  • DAR or FAR couplers can be used, which release a development accelerator or an fogger.
  • Compounds of this type are, for example, in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-89 834, 110 511, 118 087, 147 765 and described in US-A-4,618,572 and 4,656,123.
  • DIR couplers examples are:
  • DIR, DAR or FAR couplers Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-15 47 640).
  • the cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).
  • the material may further contain compounds other than couplers, which can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR-hydroquinones and other compounds, as described for example in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.
  • couplers can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR-hydroquinones and other compounds, as described for example in US-A-4 636 546, 4 345 024, 4 684 604 and in DE
  • 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. Choosing the right one Solvents or dispersants depend 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-0 043 037.
  • 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 eg dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers are e.g. 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,
  • Each of the differently sensitized, light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
  • Red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, with a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • green or red-sensitive layers are suitably low in their own sensitivity, other layer arrangements can be selected without the yellow filter layer, in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.
  • 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 from one light-sensitive layer into another light-sensitive 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.
  • Examples of particularly suitable compounds are: If there are several sub-layers of the same spectral sensitization, these can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains. In general, the sublayer with higher sensitivity will be located further from the support than the sublayer with lower sensitivity. Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, for example through Separate layers of other spectral sensitization. For example, all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).
  • 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).
  • 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.
  • binder layers in particular the most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert particles of inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).
  • photographically inert particles of inorganic or organic nature e.g. as a matting agent or as a spacer (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.
  • Suitable formalin scavengers include
  • Additives to improve the stability of dyes, couplers and whites 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.
  • 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 which react very quickly with gelatin are, for example, 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 with the formation of peptide bonds and crosslinking of the gelatin.
  • Suitable examples of instant hardeners are, for example, compounds of the general formulas wherein R1 denotes alkyl, aryl or aralkyl, R2 has the same meaning as R1 or means alkylene, arylene, aralkylene or alkaralkylene, the second bond having a group of the formula is linked, or R1 and R2 together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring can be substituted, for example, by C1-C3alkyl or halogen, R3 for hydrogen, alkyl, aryl, alkoxy, -NR4-COR5, - (CH2) m -NR8R9, - (CH2) n -CONR13R14 or or a bridge link or a direct bond to a polymer chain, wherein R4, R6, R7, R9, R14, R15, R17, R18, and R19 are hydrogen
  • 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.
  • the material is bleached and fixed immediately after color development.
  • 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.
  • development is initially carried out using a black and white developer whose oxidation product is not capable of reacting with the color couplers. This is followed by a diffuse second exposure and then development with a color developer, bleaching and fixing.
  • the layers were coated with a protective gelatin layer (0.5 ⁇ m dry layer thickness) and hardened.
  • the emulsion samples were made with 90 g (solid) of the purple latex coupler 50% by weight butyl acrylate, 20 wt .-% monomer of the formula 30 wt .-% monomer of the formula transferred.
  • the layers were coated with a gelatin protective layer (0.5 ⁇ m dry layer thickness) and hardened.
  • Three color negative layer structures were produced: 3 A structure with additives according to the invention 3 B Comparison setup with the corresponding comparison compounds 3 C comparison setup without any of the above additives.
  • the quantities given relate to 1 m2.
  • the corresponding amounts of AgNO3 are specified for the silver halide application.
  • Example 1 After imagewise exposure to white light with an exposure time of 1/100 sec. the samples were processed according to Example 1 behind a gray sensitometer wedge.
  • Table 4 This table shows the gain in sensitivity due to the additives according to the invention; this gain in sensitivity is greatest in the cyan layers (layers 3 + 4) closest to the layer support in the layer structure.
  • Table 4 Structure 3A Structure 3B Construction 3C yellow Sensitivity (DIN) 26.2 25.4 25.2 Graininess (RMS) * 27th 32 34 purple Sensitivity (DIN) 26.5 25.0 24.8 Graininess (RMS) * 10th 14 15 Blue green Sensitivity (DIN) 26.3 24.6 24.5 Graininess (RMS) * 9 15 14 * RMS granularity, measured at density 1.0 over fog

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  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19890123723 1989-01-04 1989-12-22 Matériau photographique couleur Withdrawn EP0377181A3 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0492443A1 (fr) * 1990-12-21 1992-07-01 Eastman Kodak Company Elément photographique couleur copiant à l'halogénure d'argent et procédé
EP0652474A1 (fr) * 1993-11-08 1995-05-10 Agfa-Gevaert AG Matériau photographique couleur d'enregistrement

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2879621B2 (ja) * 1991-06-18 1999-04-05 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
DE19507913C2 (de) * 1995-03-07 1998-04-16 Agfa Gevaert Ag Farbfotografisches Silberhalogenidmaterial
US6309811B2 (en) * 1999-07-21 2001-10-30 Eastman Kodak Company Color photographic element containing nitrogen heterocycle derivative and inhibitor releasing coupler

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GB2032914A (en) * 1977-08-12 1980-05-14 Ciba Geigy Ag Heterocyclyl-substituted phenacyl thioether derivatives for use as photographic development inhibitors
JPS59177555A (ja) * 1983-03-28 1984-10-08 Fuji Photo Film Co Ltd カラ−写真感光材料
DE3429545A1 (de) * 1983-08-10 1985-02-28 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Farbphotographisches lichtempfindliches silberhalogenidmaterial
EP0154293A2 (fr) * 1984-02-28 1985-09-11 Fuji Photo Film Co., Ltd. Matériel photograhique aux halogénures d'argent

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GB524557A (en) * 1938-10-26 1940-08-08 Kodak Ltd Improvements in and relating to photographic materials and the processing thereof
US2353754A (en) * 1942-11-07 1944-07-18 Eastman Kodak Co Color photography using metallic salt coupler compounds
US2401718A (en) * 1944-05-27 1946-06-04 Eastman Kodak Co Method of making coupler dispersions
US4226934A (en) * 1977-08-12 1980-10-07 Ciba-Geigy Ag Light sensitive photographic material containing development inhibitor releasing compounds

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Publication number Priority date Publication date Assignee Title
GB2032914A (en) * 1977-08-12 1980-05-14 Ciba Geigy Ag Heterocyclyl-substituted phenacyl thioether derivatives for use as photographic development inhibitors
JPS59177555A (ja) * 1983-03-28 1984-10-08 Fuji Photo Film Co Ltd カラ−写真感光材料
DE3429545A1 (de) * 1983-08-10 1985-02-28 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Farbphotographisches lichtempfindliches silberhalogenidmaterial
EP0154293A2 (fr) * 1984-02-28 1985-09-11 Fuji Photo Film Co., Ltd. Matériel photograhique aux halogénures d'argent

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Title
PATENT ABSTRACTS OF JAPAN vol. 9, no. 33 (P-334)(1756) 13 Februar 1985, & JP-A-59 177555 (FUJI SHASHIN FILM) 08 Oktober 1984, *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0492443A1 (fr) * 1990-12-21 1992-07-01 Eastman Kodak Company Elément photographique couleur copiant à l'halogénure d'argent et procédé
EP0652474A1 (fr) * 1993-11-08 1995-05-10 Agfa-Gevaert AG Matériau photographique couleur d'enregistrement

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EP0377181A3 (fr) 1991-06-12
US5158864A (en) 1992-10-27
JPH02228651A (ja) 1990-09-11

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