EP0672948A2 - Fotografisches Aufzeichnungsmaterial - Google Patents

Fotografisches Aufzeichnungsmaterial Download PDF

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Publication number
EP0672948A2
EP0672948A2 EP95102880A EP95102880A EP0672948A2 EP 0672948 A2 EP0672948 A2 EP 0672948A2 EP 95102880 A EP95102880 A EP 95102880A EP 95102880 A EP95102880 A EP 95102880A EP 0672948 A2 EP0672948 A2 EP 0672948A2
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EP
European Patent Office
Prior art keywords
coupler
silver halide
color
halide emulsion
color photographic
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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Application number
EP95102880A
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German (de)
English (en)
French (fr)
Other versions
EP0672948A3 (enrdf_load_stackoverflow
Inventor
Günther Dr. Helling
Beate Dr. Weber
Helmut Dr. Reiff
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication of EP0672948A2 publication Critical patent/EP0672948A2/de
Publication of EP0672948A3 publication Critical patent/EP0672948A3/de
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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
    • 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 photographic recording material with at least one silver halide emulsion layer, which contains certain polymers as oil formers for the image dyes produced during chromogenic development, in particular for purple azomethine dyes.
  • color couplers can be dispersed in water-insoluble, organic solvent-soluble polymers.
  • No. 4,388,403 describes a process for the production of dispersions of hydrophobic substances in water, in which color couplers are applied to ionomeric polyurethanes by means of a loading process. It is disadvantageous that the particles loaded with couplers are not sufficiently stable and, in particular, pyrazolotriazole couplers crystallize out within a short time.
  • the invention is based on the object of providing novel polymers which, as oil formers, contribute to improving the maximum densities, reducing undesirable secondary densities from the couplers, improving white stability when stored in the heating cabinet and avoiding undesirable secondary densities when irradiated.
  • the invention therefore relates to a color photographic material which contains on a support at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler and conventional non-light-sensitive layers. characterized in that at least one layer contains a non-ionic, essentially aliphatic polyurethane of molecular weight (number average) 3,000 to 50,000, preferably 8,000 to 40,000.
  • the molecular weight (number average) is measured according to L.M. Peebles, Molecular Weight Distributions in Polymers, Interscience 1971, p. 207.
  • Substantially aliphatic means that no more than 10% by weight of the total amount of the starting substances is aromatic starting substances.
  • the proportion of aromatic starting substances is preferably at most 5% by weight.
  • 0.1 to 3 g / g coupler of the layer in question preferably 0.5 to 1 g / g coupler of polyurethane are used and the polyurethane is used in a coupler-containing silver halide emulsion layer.
  • the polyurethanes according to the invention are preferably used in the layer or layers which contain magenta couplers.
  • the polyurethanes can be produced in the melt in a manner known per se or, preferably, in an organic solvent.
  • polyisocyanates of the formula Q (NCO) 2 are used, Q being an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon radical having 6 to 25 carbon atoms, an aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical 7 to 15 carbon atoms.
  • diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanato-cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 4,4'-diisocyanylmethanicyclo Diisocyanato-3,3'-dimethyl-dicyclohexylmethane, 4,4'-diisocyanatodicyclohexylpropane- (2,2), 1,4-diisocyanatobenzene, 2,4- or 2,6-diisocyanatotoluene or mixtures of these isomers, 4,4 '-, 2,4'- or 2,2'-diisocyanatodiphenylmethane or mixtures of the isomers,
  • polyisocyanates known per se in polyurethane chemistry or else modified ones known per se, for example carbodiimide groups, allophanate groups, isocyanurate groups, To use urethane groups and / or biuret groups polyisocyanates (with).
  • the most suitable reaction partners for the polyisocyanates are polyhydroxyl compounds which have 1 to 8, preferably 1 to 3, hydroxyl groups per molecule and have an (average) molecular weight of up to 5000, preferably up to 3500. Both low molecular weight polyhydroxyl compounds with molecular weights of 32 to 349 and higher molecular weight polyhydroxy compounds with average molecular weights of at least 350, preferably of at least 1000, are suitable, as are described in detail in the abovementioned publications.
  • Higher molecular weight polyhydroxyl compounds include the hydroxypolyesters, hydroxypolyethers, hydroxypolythioethers, hydroxypolyacetals, hydroxypolycarbonates and / or hydroxypolyesteramides known per se in polyurethane chemistry, preferably those with average molecular weights from 600 to 4000, particularly preferably those with average molecular weights from 800 to 2500.
  • Polycarbonate polyols, polyether polyols and polyester polyols are particularly preferred.
  • Polyhydroxyl components which are suitable as polyurethane structural components are described below.
  • the suitable polycarbonates containing hydroxyl groups can be obtained by reacting carbonic acid derivatives, for example diphenyl carbonate or phosgene, with diols.
  • diols are ethylene glycol, 1,2-and 1,3-propanediol, 1,4-and 1,3-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2 -Methyl-1,3-propanediol, 2,2,4-trimethylpentanediol-1,3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A, tetrabromobisphenol A in question.
  • the diol component preferably contains 40 to 100% by weight of hexanediol, preferably 1,6-hexanediol, and / or hexanediol derivatives, preferably those which, in addition to terminal OH groups, have ether or ester groups, for example products obtained by reaction of 1 mol of hexanediol with at least 1 mol, preferably 1 to 2 mol of caprolactone according to DE-AS 17 70 245, or by etherification of hexanediol with itself to give di- or trihexylene glycol.
  • the preparation of such derivatives is known, for example, from DE-AS 1 570 540.
  • the polyether polycarbonate diols described in DE-OS 37 17 060 can also be used very well.
  • the hydroxyl polycarbonates are said to be substantially linear. If desired, however, they can easily be branched by incorporating polyfunctional components, in particular low molecular weight polyols.
  • polyfunctional components in particular low molecular weight polyols.
  • glycerol, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, methylglycoside, 1,4,3,6-dianhydrohexite are suitable for this purpose.
  • Suitable polyether polyols are the polyethers known per se in polyurethane chemistry, such as e.g. the addition or mixed addition compounds of tetrahydrofuran, styrene oxide, propylene oxide, butylene oxides or epichlorohydrin, especially propylene oxide, produced using divalent starter molecules such as water, the above-mentioned diols or amines having 2 NH bonds.
  • Particularly preferred polyethers are OH-terminated polytetrahydrofurans with a molecular weight of 500 to 2500.
  • Suitable polyester polyols are, for example, reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric, carboxylic acids.
  • polyhydric preferably dihydric and optionally additionally trihydric alcohols
  • polyhydric preferably dihydric, carboxylic acids.
  • the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof can also be used to produce the polyesters.
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms, and / or unsaturated.
  • Examples include: Succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, terephthalic acid dimethyl ester, Terephthalic acid bis-glycol ester.
  • polyhydric alcohols are e.g. Ethylene glycol, propanediol- (1,2) and - (1,3), butanediol- (1,4) and - (2,3), hexanediol- (1,6), octanediol- (1,8), neopentylglycol, Cyclohexanedimethanol (1,4-bis-hydroxymethyl-cyclohexane), 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4), trimethylolethane, pentaerythritol , Quinite, mannitol and sorbitol, methyl glycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, dibutylene glycol and polybutylene glycol in question.
  • Chain extenders with molecular weights of 32 to 299 and having 1-4 hydroxyl and / or amino groups are particularly suitable as additional structural components for the production of the polyurethanes.
  • polyamines can also be used as chain extenders. These are preferably aliphatic or cycloaliphatic diamines, although trifunctional or higher-functional polyamines can optionally also be used to achieve a certain degree of branching.
  • suitable aliphatic polyamines are ethylenediamine, 1,2-and 1,3-propylenediamine, 1,4-tetramethylenediamine, 1,6-hexamethylenediamine, the mixture of isomers of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2- Methyl pentamethylene diamine and bis ( ⁇ -aminoethyl) amine (diethylene triamine).
  • Suitable cycloaliphatic polyamines are: Araliphatic polyamines such as 1,3- and 1,4-xylylenediamine or ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3- and -1,4-xylylenediamine can also be used as chain extenders for the production of the polyurethanes .
  • Hydrazine, hydrazine hydrate and substituted hydrazines such as e.g.
  • Methylhydrazine, N, N'-dimethylhydrazine and their homologs and acid dihydrazides such as carbodihydrazide, oxalic dihydrazide, the dihydrazides of malonic acid, succinic acid, glutaric acid, adipic acid, ⁇ -methyladipic acid, sebacic acid, hydracrylic acid and terephthalic acid, semicarbazido-alkylene-hydrazide as e.g.
  • ⁇ -semicarbazido-propionic acid hydrazide (DE-OS 17 70 591), semicarbazido-alkylene carbazine esters, such as 2-semicarbazidoethyl-carbazine ester (DE-OS 19 18 504) or amino-semicarbazide compounds, such as ⁇ -aminoethylsemicarbazido carbonate ( DE-OS 19 02 931).
  • the polyurethanes are produced in a manner known per se:
  • the polyisocyanate is added to the dehydrated polyhydroxyl compound at room temperature to 60 ° C. with stirring and under nitrogen.
  • the mixture is heated to 70 to 120 ° C. and held at this temperature for 0.5 to 5 hours. Now, if necessary, with a tert. Amine or a tin compound catalyzed and the NCO content determined.
  • the material is dissolved in a solvent, preferably in ethyl acetate, and the calculated amount of chain terminator (blocking agent) is added.
  • the mixture is optionally stirred at 50 to 70 ° C until the NCO content is 0.
  • reaction products are low-viscosity, it is also possible, if appropriate, to work without a solvent.
  • hydrophilic structural components can be incorporated into the NCO prepolymers. This can be done, for example, by using compounds which have (i) at least one group which is reactive toward isocyanate groups, preferably an alcoholic hydroxyl group, and (ii) nonionic-hydrophilic polyoxyethylene units.
  • Such structural components are described, for example, in US Pat. No. 3,905,929, US Pat. No. 4,190,566 or US Pat. No. 4,237,264.
  • hydrophilically modified polyisocyanates in addition to the above-mentioned polyisocyanates which are not hydrophilically modified as a further polyisocyanate component use, for example those of the type described in US Pat. No. 3,920,598 or those such as those obtained by reacting excess amounts of organic polyisocyanates of the type mentioned above with hydrophilic structural components groups of the latter type which are reactive toward isocyanate groups can be obtained.
  • NCO prepolymers In the preparation of the NCO prepolymers, the starting materials mentioned are generally maintained with an equivalent ratio of isocyanate groups to isocyanate-reactive groups of 1.1: 1 to 3: 1, preferably 1.1: 1 to 2: 1 at temperatures of 20 to 150 ° C, preferably 60 to 120 ° C reacted with each other. From the above-mentioned information regarding the equivalent ratio of the reactants, it is already clear that "NCO prepolymers" within the scope of the present invention also include so-called “semiprepolymers", i.e. Mixtures of real prepolymers with excess amounts of starting isocyanates are to be understood.
  • the polyisocyanate component can be used in (partially) blocked form when carrying out the synthesis for the purpose according to the invention.
  • Suitable blocking agents or chain terminators are, for example, lactams such as ⁇ -caprolactam, oximes such as acetone oxime, methyl ethyl ketone oxime (butanone oxime) and cyclohexanone oxime, CH-acidic compounds such as diethyl malonate, ethyl acetoacetate and acetylacetone, alcohols such as the simple monoalcohols with 1 to 14 alcohols -Ethylhexanol, ethylene glycol monoethyl ether and diethylene glycol monoethyl ether, phenols such as phenol, cresol and xylenol and heterocyclic compounds such as triazoles, imidazolines, imidazoles and tetrahydropyrimidines.
  • blocking agents described can be used alone or in the form of mixtures.
  • Preferred blocking agents are butanone oxime, diethanolamine, N-alkylethanolamines, N, N-dialkylethanolamines, aliphatic dialkylamines such as, for example, dimethylamine, diethylamine, diisopropylamine, dibutylamine, etc.
  • the partial blocking of the polyisocyanate component used in the process according to the invention can take place in the presence or absence of solvents, for example acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, toluene, xylene and / or aliphatic hydrocarbon solvents. Is ethyl acetate a particularly preferred solvent.
  • the blocking reaction is generally carried out at temperatures up to 150 ° C., preferably at 20 to 100 ° C. If partially blocked NCO prepolymers are used as the polyisocyanate component, partial blocking is generally carried out simultaneously or after the preparation of the NCO prepolymers.
  • the NCO functionality of the partially blocked polyisocyanates, i.e. the number of free isocyanate groups present on average per molecule in the polyisocyanate is generally 1.8 to 2.3.
  • Preferred polyurethanes are produced from polyesters or polyethers on the one hand, hexamethylene diisocyanate, isophorone diisocyanate or 3,3,5-trimethylhexamethylene diisocyanate on the other hand and monofunctional, aliphatic chain terminators.
  • the polyisocyanate is added to the dehydrated polyhydroxyl compound at 40.degree.
  • the mixture is heated to 105 ° C. and held at this temperature for 1.5 hours. Now catalyze with 1 drop of dibutyltin dilaurate and determine the NCO content.
  • the material is dissolved 40% in ethyl acetate and the calculated amount of chain terminator (blocking agent) is added.
  • the batch is optionally stirred at 55 ° C.
  • the NCO prepolymer from Example 13 is repeated.
  • the NCO content was 0.44%.
  • the prepolymer (1400 g) was diluted to 50% with ethyl acetate and divided into 5 portions of 500 g each.
  • the chain termination was carried out with the chain terminators listed in the following table. After the NCO value had dropped to zero, the mixture was adjusted to 40% solids with further ethyl acetate.
  • the silver halide present as a light-sensitive component in the photographic recording material according to the invention 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.
  • It can be predominantly compact crystals, 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 in which the ratio of diameter to thickness is substantially greater than 5: 1, for example 12: 1 to 30: 1.
  • the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different.
  • the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be either homodisperse or 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 other silver salts, e.g. contain organic silver salts such as silver benzotriazolate or silver behenate.
  • Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
  • the emulsions can be chemically and or spectrally sensitized in the usual way; they can also be stabilized by suitable additives. Suitable chemical sensitizers, spectral sensitizing dyes and stabilizers are described, for example, in Research Disclosure 17643 (December 1978); Reference is made in particular to chapters III, IV and VI.
  • the color photographic recording material according to the invention preferably contains, in addition to the silver halide emulsion layer which is normally green-sensitized and contains the combination of magenta coupler and polyurethane according to the invention, further silver halide emulsion layers for recording light in the spectral ranges red and blue.
  • the light-sensitive layers are spectrally sensitized in a known manner by means of suitable sensitizing dyes.
  • Suitable green sensitizers are, for example, 9-ethylcarbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzothiazole 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.
  • Each of the said photosensitive layers can consist of a single layer or in a known manner, e.g. in the so-called double-layer arrangement, also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
  • red-sensitive silver halide emulsion layers are usually arranged closer to the support than green-sensitive silver halide emulsion layers and these in turn are closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • other arrangements are also conceivable, e.g. for color paper.
  • a non-light-sensitive intermediate layer is generally arranged between layers of different spectral sensitivity and can contain means for preventing the incorrect diffusion of developer oxidation products. If there are several silver halide emulsion layers of the same spectral sensitivity, they can be directly adjacent to one another or be arranged such that there is a light-sensitive layer with a different spectral sensitivity between them (DE-A-1 958 709, DE-A-2 530 645, DE-A -2 622 922).
  • Color photographic recording materials according to the invention usually contain, in spatial and spectral assignment to the silver halide emulsion layers of different spectral sensitivity, color couplers for producing the different partial color images cyan, magenta and yellow, the inventive ones Connections together with the respective color coupler are preferably assigned to a green-sensitive silver halide emulsion layer.
  • the color coupler is in such a spatial relationship with the silver halide emulsion layer that an interaction between them is possible which permits an image-wise correspondence between the silver image formed during development and the color image generated from the color copter. This is usually achieved by the fact that the color coupler is contained in the silver halide emulsion layer itself or in an adjacent, possibly non-light-sensitive binder layer.
  • Spectral assignment is to be understood to mean that the spectral sensitivity of each of the light-sensitive silver halide emulsion layers and the color of the partial color image generated from the spatially assigned color coupler are in a specific relationship, each of the spectral sensitivities (red, green, blue) having a different color of the relevant partial color image (in general, for example, the colors cyan, magenta or yellow in this order).
  • Each of the differently spectrally sensitized silver halide emulsion layers can be assigned one or more color couplers. If there are multiple silver halide emulsion layers of the same spectral sensitivity, each of them may contain a color coupler, although these color couplers need not necessarily be identical. They should only result in at least approximately the same color during color development, normally a color that is complementary to the color of the light to which the silver halide emulsion layers in question are predominantly sensitive.
  • Teal couplers are usually couplers of the phenol or ⁇ -naphthol type.
  • Yellow couplers are usually couplers with an open-chain ketomethylene group, in particular couplers of the ⁇ -acylacetamide type, for example benzoylanilide couplers and ⁇ -pivaloylacetanilide couplers.
  • Purple couplers are typically 5-pyrazolone, indazolone or pyrazoloazole type couplers.
  • Couplers of the formula I are referred to collectively as pyrazoloazole couplers. These are understood to mean in particular couplers which are derived from imidazolo [1,2-b] pyrazole, imidazolo [3,4-b] pyrazole, pyrazolo [2,3-b] pyrazole, pyrazolo [3,2-c] -1 , 2,4-triazole, pyrazolo [2,3-b] -1,2,4-triazole, pyrazolo [2,3-c] -1,2,3-triazole or Pyrazolo [2,3-d] tetrazole.
  • the corresponding structures are given below by the formulas Ia to Ig.
  • the radicals R10, R12, R13 and R14 represent hydrogen, alkyl, aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, carbamoyl, sulfamoyl, these being Residues can be further substituted.
  • R11 radicals which can be split off in the color coupling are e.g. a halogen atom or a preferably cyclic group attached to the coupling point via an oxygen atom, a sulfur atom or a nitrogen atom.
  • the coupling to the coupling point of the coupler molecule can either be directly via an atom which is part of a ring, e.g. B. a nitrogen atom, or indirectly via an intermediate link.
  • Such cleavable groups are known in large numbers, for. B. as escape groups of 2 equivalent magnetic couplers.
  • cleavable groups attached via oxygen correspond to the formula -O-R15, wherein R15 represents an acyclic or cyclic organic radical, for example alkyl, aryl, a heterocyclic group or acyl, which is derived for example from an organic carbon or sulfonic acid.
  • R15 represents an acyclic or cyclic organic radical, for example alkyl, aryl, a heterocyclic group or acyl, which is derived for example from an organic carbon or sulfonic acid.
  • R15 represents an optionally substituted phenyl group.
  • heterocyclic rings which are connected to the coupling site of the purple coupler via a ring nitrogen atom.
  • the heterocyclic rings often contain groups adjacent to the nitrogen atom activating the bond to the coupler molecule, e.g. B. carbonyl or sulfonyl groups or double bonds.
  • the cleavable group is attached to the coupling site of the coupler via a sulfur atom, it can be the remainder of a diffusible carbocyclic or heterocyclic mercapto compound which is able to inhibit the development of silver halide.
  • Such inhibitor residues have been widely described as a cleavable group attached to the coupling site of couplers, including magenta couplers, e.g. in US-A-3,227,554.
  • pyrazoloazole couplers those of the formulas Id and Ie are preferred.
  • at least one of the radicals R10 and R13 is a secondary alkyl or tertiary alkyl radical.
  • 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 point, which is split off during the coupling.
  • the 2-equivalent couplers include those that are colorless, as well as those that have an intensive intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), but also the white couplers that are used Reaction 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 (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 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.
  • the couplers used in particular the magenta couplers of the pyrazoloazole type, preferably used according to the invention, for example of the formulas Id and Ie, can also be in polymeric form, e.g. are used as polymer latex.
  • 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.
  • the color couplers used can also be those which provide dyes with poor or restricted mobility.
  • Weak or restricted mobility means mobility that is dimensioned such that the contours of the discrete dye spots formed in the chromogenic development run and are smeared into one another.
  • This degree of mobility must be distinguished on the one hand from the usual case of complete immobility in photographic layers, which is sought in conventional photographic recording materials for the color couplers or the dyes produced therefrom, in order to achieve the highest possible sharpness, and on the other hand from the case of complete mobility of the dyes, which is sought, for example, in color diffusion processes.
  • the last-mentioned dyes usually have at least one group that make them soluble in the alkaline medium.
  • the extent of the weak mobility sought according to the invention can be controlled by varying substituents, for example in order to influence the solubility in the organic medium of the oil former or the affinity for the binder matrix in a targeted manner.
  • the color photographic recording material of the present invention can contain further additives, for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties and UV absorbers.
  • additional compounds are advantageously combined with the compounds according to the invention, i.e. used in the same binder layer or in adjacent binder layers.
  • 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).
  • the color photographic recording material according to the invention which, in association with at least one silver halide emulsion layer, contains a magenta coupler and a combination of a compound of the formula I and a polyurethane, is developed with a color developer compound.
  • All developer compounds which have the ability in the form of their oxidation product to react with color couplers to form azomethine 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-methylsulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl-3-methyl-p-phenylenediamine, 1- (N-ethyl-N- [3-hydroxypropyl]) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-
  • the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together.
  • the usual compounds can be used as bleaching agents, for example Fe3+ salts and Fe3+ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes, etc.
  • Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediamine triacetic acid, alkyliminodicarboxylic acids and alkyliminodicarboxylic acids and Phosphonic acids.
  • Persulphates are also suitable as bleaching agents.
  • Samples 2 to 9 were produced in the same way as sample 1, with the difference that the polyester A used in sample 1 was replaced by one of the compounds according to the invention (see Table 1).
  • the samples obtained were then exposed behind a graduated gray wedge.
  • the materials were then processed in the following manner using the processing baths listed below: Development: 210 s, 33 ° C Bleaching: 50 s, 20 ° C Fix: 60 s, 20 ° C Water: 120 s, 20 ° C Dry.
  • a layer structure is produced as in Example 1, with the difference that the polymer S-1 (sample 16) is used as an emulsifying additive as a comparative polymer from DE-OS 4 136 965.
  • Samples 10 to 15 are produced in the same way, with the difference that the compounds according to the invention are used instead of the polymer S-1.
  • the samples are processed as described in Example 1. Then the gb-veil after 50 days storage at 80 ° C 50% r. F. measured (Table 2). Table 2 Heating cabinet storage 21 d at 80 ° C 50% r. F.
  • sample polymer Veil gb 10th P1 0.10 11 P2 0.10 12th P3 0.10 13 P7 0.10 14 P8 0.10 15 P11 0.10 16 S-1 0.16 S-1 reaction product of 2-amino-4-methylphenol and an NCO prepolymer made of a polyester composed of adipic acid and butanediol reacted with hexamethylene diisocyanate (in accordance with DE 4 136 965).
  • a layer structure is produced as in Example 1, with the difference that polyester A, stabilizer St 1 and stabilizer St 2 (sarison).
  • Samples 18 to 20 are produced in the same way, with the difference that the polymers according to the invention are used instead of polyester A.
  • the samples are processed according to Example 1.
  • the yellowing in the image whites is then measured after storage for 42 days at 80 ° C. and 50% rh as a fog (Table 3).
  • Table 3 shows that the yellowing of the photographic material can be reduced with the polymers according to the invention.
  • a color coupler emulsifier is prepared by dissolving a solution of 7.5 g of coupler I-6 and 7.5 g of polymer P1 (sample 21) in 20 ml of ethyl acetate at 40 ° C. and in 125 g of a 6% strength by weight aqueous solution Gelatin solution containing 0.75 mg Contains dodecanylbenzenesulfonate, emulsified for 5 minutes at 17000 rpm using a mixed siren. The emulsifier obtained is cooled to RT and examined for particle size and crystal deposits. Samples 22 to 30 are made in the same manner, except that other polymers and couplers are used.
  • polyurethanes according to EP 49 399 are loaded with the same color couplers and the same coupler / polymer ratio. Particle size and crystallization behavior are also checked.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP95102880A 1994-03-14 1995-03-01 Fotografisches Aufzeichnungsmaterial Withdrawn EP0672948A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19944408477 DE4408477A1 (de) 1994-03-14 1994-03-14 Fotografisches Aufzeichnungsmaterial
DE4408477 1994-03-14

Publications (2)

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EP0672948A2 true EP0672948A2 (de) 1995-09-20
EP0672948A3 EP0672948A3 (enrdf_load_stackoverflow) 1995-11-02

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EP95102880A Withdrawn EP0672948A2 (de) 1994-03-14 1995-03-01 Fotografisches Aufzeichnungsmaterial

Country Status (3)

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EP (1) EP0672948A2 (enrdf_load_stackoverflow)
JP (1) JPH07281375A (enrdf_load_stackoverflow)
DE (1) DE4408477A1 (enrdf_load_stackoverflow)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1522387A1 (de) * 1966-07-02 1969-07-24 Agfa Gevaert Ag Photographische,gelatinehaltige Schichten mit verbesserten physikalischen Eigenschaften
JP2896437B2 (ja) * 1988-01-12 1999-05-31 富士写真フイルム株式会社 ハロゲン化銀カラー感光材料
DE4136965A1 (de) * 1991-11-11 1993-05-13 Agfa Gevaert Ag Fotografisches aufzeichnungsmaterial

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EP0672948A3 (enrdf_load_stackoverflow) 1995-11-02
DE4408477A1 (de) 1995-09-21
JPH07281375A (ja) 1995-10-27

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