EP0373339B1 - Matériau d'enregistrement photosensible à l'halogénure d'argent - Google Patents

Matériau d'enregistrement photosensible à l'halogénure d'argent Download PDF

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EP0373339B1
EP0373339B1 EP89120323A EP89120323A EP0373339B1 EP 0373339 B1 EP0373339 B1 EP 0373339B1 EP 89120323 A EP89120323 A EP 89120323A EP 89120323 A EP89120323 A EP 89120323A EP 0373339 B1 EP0373339 B1 EP 0373339B1
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alkyl
hydrogen
compounds
silver halide
substituted
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EP0373339A1 (fr
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Manfred Dr. Becker
Hans Dr. Öhlschläger
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • the invention relates to a silver halide recording material with improved latent image stabilization.
  • latent image stabilizers are added to the photographic materials, which are intended to prevent the latent image from degrading over long periods of time.
  • Examples of compounds which are intended to act as latent image stabilizers are, for example, in GB 1 308 777, DE 2 325 039, 2 335 093, 2 304 322, 3 308 203, JA 50/94918, 57/100 424, JP 116 167, GB 1 458 197 and US 4,334,014 and 4,378,426.
  • the known compounds which are intended to stabilize the latent image of photographic emulsions, have the disadvantage that, depending on the amount added per mole of silver halide (and depending on the pH and pAg of the emulsion layer) when the exposed emulsion is stored, either the decrease in the latent image is insufficient slow down or stabilize the latent image to a satisfactory extent, but at the same time cause the fog of the photographic emulsion to increase to an increased extent during storage.
  • anti-fogging agents e.g. 5-methyl-benzotriazole, 1-phenyl-5-mercapto-tetrazole, 2,5-dimercapto-1,3,4-thiadiazole etc.
  • antifoggants are able to inhibit the increase in fog caused by the latent image stabilizers during storage, without breaking latent image stabilization.
  • a disadvantage of this latent image stabilization method is that the antifoggants have to be added in amounts which significantly reduce the sensitivity of the emulsion.
  • the object of the invention was therefore to find measures to effectively stabilize the latent image and at the same time to minimize the increase in fog and loss of sensitivity.
  • the object is achieved in that the silver halide emulsions of the photographic material are each added at least one compound from at least two different classes of substances specified below.
  • Heterocyclic systems of the formula II are, for example, benzoxazole, naphtha [1,2: d] oxazole, naphtha [2,3: d] oxazole, naphtha [2,1: d] oxazole, oxazine, naphtha [1,8: de] oxazine .
  • the oxazole or oxazine rings contain substituents with acidic groups or fused aromatic rings with preferably attached acidic groups, examples of acidic groups are -COOH and -SO3H groups.
  • the compounds of the formula II can be further substituted by halogen atoms, alkyl, ether and ester groups.
  • the emulsions can contain further antifoggants and stabilizers.
  • Azaindenes are particularly suitable, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are described, for example, in the article by Birr, Z. Wiss. Phot. 47 , (1952), pp. 2-58.
  • Additional stabilizers and antifoggants such as those listed in Research Disclosure No. 17643 of December 1978, Section VI, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, PO9 1 EF in Great Britain, can be added insofar as they are do not interfere with the action according to the invention of the compounds of classes A, B, C and D.
  • the silver halide recording material according to the invention can be a black and white or a color photographic material.
  • 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 foils 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 carriers 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, 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, are examples of this.
  • the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
  • functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
  • the gelatin which is preferably used can be obtained by acidic or alkaline digestion. It can also oxidized gelatin can be used. The preparation of such gelatins is 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.
  • 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, where the ratio of diameter to thickness is much 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 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 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 by physical ripening (Ostwald ripening) in the presence of excess halide and / or silver halide complexing agent.
  • the growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.
  • Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe may 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 can be carried out with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid) using hydrogen, by means of low pAg (eg less than 5) and / or high pH (eg above 8) .
  • reducing agents titanium-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid
  • 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.).
  • surface-active compounds e.g. saponin
  • non-ionic surfactants e.g. alkylene oxide compounds, glycerol compounds or glycidol compounds
  • cationic surfactants e.g.
  • 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 as well as sulfuric 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.
  • red sensitizers RS examples, in particular for negative and reversal film, are the red sensitizers RS, green sensitizers GS and blue sensitizers BS, which can be used individually or in combination with each other, e.g. RS 1 and RS 2, and GS 1 and GS 2.
  • 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 become cyan couplers, assigned to the green-sensitive layers of purple couplers and the blue-sensitive layers of yellow couplers.
  • white couplers are:
  • mask 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.
  • 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.
  • DIR couplers in particular those which release an easily diffusible development inhibitor
  • suitable measures can be taken to improve the color rendering, e.g. achieve a more differentiated color rendering, as described, for example, in EP-A-115 304, 167 173, GB-A-2 165 058, DE-A-37 00 419 and US-A-4 707 436.
  • 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 use a DIR coupler which forms in the respective layer in which it is introduced a color which is different from the color to be produced 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 are: Examples of DAR couplers Since with DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is 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 are dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert.-amylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-doxy-5-butyl-2-butyl
  • 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, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • the green or Red-sensitive layers can be selected without the yellow filter layer, other layer arrangements 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.
  • 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).
  • 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 whiteners 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 H2N-CONH- (CH2) 2-NH-CONH2, Additives to improve dye, coupler and whiteness stability and to reduce the color fog (Research Disclosure 17 643/1978, Chapter VII) can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes, p- Alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
  • hydroquinones 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes, p- Alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amine
  • the layers of the photographic material can be hardened with the usual hardening agents.
  • Suitable curing agents include formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen contain (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207) divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5 triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732 316 and US
  • the hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened, or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
  • Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed immediately after casting, at the latest after 24 hours, preferably after 8 hours at the latest, so 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.
  • 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, which contain at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfone-amidoethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • Other 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.
  • Persulfates 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 acts as a final bath.
  • the film samples were exposed in a sensitometer behind a 3 ⁇ 2 step gray wedge, the development at 20 ° C in a commercially available black and white developer (refinal) for 16 minutes.
  • a second sample was exposed, then stored for 14 days at 57 ° C. and 35% relative humidity and then processed;
  • a third sample was stored at 57 ° C. and 35% relative humidity for 14 days before exposure, then exposed and processed within 6 hours after exposure.
  • Table 1 shows that the compounds A-3, A-4, A-23 and B-8 individually have a more or less stabilizing effect on the latent image, but significantly reduce the sensitivity of the fresh material.
  • the sensitivity is always higher, although on the entire amount of latent image stabilizer nothing was changed per mole of silver halide (namely 600 ⁇ mol / molAg).
  • latent image stabilizations with the combinations of a compound of the compound classes A and C each show a higher sensitivity than the latent image stabilizations with the respective compounds of the compound class A alone, as a comparison with Table 1 shows; latent image stabilization with C-4 alone is weaker than with A-3, A-4, A-23 or B-8 alone and leads to higher fog at the same time.
  • connection classes A, B, and C provide somewhat higher sensitivities than the two-combination, while the stabilization of the latent image is retained.
  • Example 3 The results shown in Table 3 are obtained with a compound from compound class D and the emulsion given in Example 1. Analogously to Example 2, it is found that it is advantageous not to use a compound with a latent image stabilizing effect individually, but for combinations of compounds from two different classes of compounds (A + D or B + D) or from three different classes of compounds (A + B + D).

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Claims (4)

  1. Matériau photosensible à l'halogénure d'argent comportant un support et au moins une couche photosensible d'émulsion à l'halogénure d'argent, dont l'émulsion contient au moins un composé d'au moins deux des classes de composés A, B, C et D indiquées ci-après, en quantité efficace :
    A) Composés de formule générale :
    Figure imgb0133
     dans laquelle
    R₁   représente l'hydrogène, un groupe alkyle ayant jusqu'à 9 atomes de carbone, qui peut être substitué, un groupe aryle, aralkyle, cycloalkyle ou un hétérocycle,
    R₂   représente de l'hydrogène, un groupe alkyle qui peut être substitué ou non substitué, un groupe alcényle, aryle ou -NR₄R₅ ;
    R₃   est de l'hydrogène ou un groupe éliminable au cours du développement
    R₄, R₅   représentent R₁, -COR₆, -CONHR₇ ou -COOR₈ ;
    R₆   est un groupe alkyle ou cycloalkyle ayant jusqu'à 8 atomes de carbone, qui peut être substitué ou non substitué, un groupe allyle, benzyle ou aryle ;
    R₇   est de l'hydrogène ou un groupe R₆ ;
    R₈   est un groupe alkyle ou cycloalkyle ayant jusqu'à 8 atomes de carbone, qui peut être substitué ou non substitué ; ou un groupe aryle,
    B) Composés de formule générale
    Figure imgb0134
     ou des tautomères de ces composés, formule dans laquelle
    Z   représente les atomes nécessaires pour compléter un noyau d'oxazole ou d'oxazine et
    Y   est un système cyclique aromatique condensé ayant au moins un noyau aromatique qui est substitué avec au moins un groupe acide ;
    C) Composés de formule générale
    Figure imgb0135
     dans laquelle
    R₁₁, R₁₂   sont identiques ou différents et représentent de l'hydrogène ou un groupe alkyle en C₁ à C₃,
    R₁₃, R₁₄   sont identiques ou différents et représentent de l'hydrogène, un groupe alkyle en C₁ à C₆, cycloalkyle, aryle, un hétérocycle, un groupe carboxyle ou un groupe aminocarbonyle et
    n   a la valeur 1 ou 2 ; et
    D) Composés de formule générale
    Figure imgb0136
     dans laquelle
    R₁₅   représente de l'hydrogène, un groupe alkyle en C₁ à C₈ qui peut être substitué ou non substitué, un groupe allyle ; un groupe benzyle ; un groupe de formule -COR₂₀, -COOR₂₁ ou
    Figure imgb0137
    R₁₆, R₁₇   représentent de l'hydrogène ou un groupe alkyle en C₁ à C₃,
    R₁₈   représente de l'hydrogène, un groupe -COR₂₂, -CONHR₂₃ ;
    R₁₉   est de l'hydrogène ou un groupe alkyle en C₁ à C₁₀,
    R₂₀, R₂₁, R₂₂   représentent un groupe alkyle ou un groupe cycloalkyle ayant jusqu'à 8 atomes de carbone, qui peut être substitué, un groupe benzyle, allyle ou aryle,
    R₂₃   est de l'hydrogène ou un groupe R₂₀
    X   est une liaison directe ou un groupe alkylène ayant jusqu'à 6 atomes de carbone et
    m   a la valeur 0 ou 1.
  2. Matériau photosensible à l'halogénure d'argent suivant la revendication 1, dans lequel, dans les composés A
    R₁   représente de l'hydrogène, un groupe alkyle en C₁ à C₉, non substitué ou portant un substituant alkoxy en C₁ à C₄, carboxy, hydroxy, halogéno, (alkoxy en C₁ à C₄)carbonyle, (alkyle en C₁ à C₄)carbonyloxy ou phénoxy, un groupe phényle, non substitué ou portant un substituant alkyle en C₁ à C₄, alkoxy en C₁ à C₄ ou halogéno, un groupe cyclohexyle, benzyle, pyrridyle ou furyle,
    R₂   représente de l'hydrogène, un groupe alkyle en C₁ à C₄ portant éventuellement un substituant carboxy, (alkoxy en C₁ à C₄)carbonyle ou 1-pipéridino, un groupe allyle, phényle ou -NR₄R₅,
    R₃   est de l'hydrogène, un groupe (alkyle en C₁ à C₄)carbonyle ou (alkoxy en C₁ à C₆)carbonyle,
    R₄   est de l'hydrogène, un groupe (alkyle en C₁ à C₄)carbonyle, hydroxyéthyle, (alkyle en C₁ à C₄)aminocarbonyle, cyclohexylaminocarbonyle, sulfophényle, sulfophénylcarbonyle, méthylmercaptoacétyle ou (alkoxy en C₁ à C₄)carbonyle,
    R₅   est de l'hydrogène, un groupe (alkyle en C₁ à C₄)carbonyle ou (alkoxy en C₁ à C₄)carbonyle ;
    les composés B répondent à la formule
    Figure imgb0138
     dans laquelle
    R₂₄ à R₂₇   sont identiques ou différents et représentent de l'hydrogène ou un groupe alkyle et deux des substituants R₂₄-R₂₇ peuvent former conjointement le reste complétant un noyau, sous réserve que l'un au moins des substituants R₂₄ à R₂₇ contienne un substituant acide ou soit un substituant acide ;
    dans les composés C
    R₁₁ et R₁₂   représentent indépendamment l'un de l'autre de l'hydrogène ou un groupe méthyle,
    R₁₃   est de l'hydrogène ou un groupe méthyle,
    R₁₄   est de l'hydrogène, un groupe méthyle, furyle, méthylfuryle, thiényle, bromothiényle, cyclohexyle, phényle, carboxy ou aminocarbonyle et
    n   a la valeur 1 ou 2, et
    dans les composés D
    R₁₅   est de l'hydrogène, un groupe alkyle en C₁ à C₄, carboxy-(alkyle en C₁ à C₄), allyle, (alkoxy en C₁ à C₄)carbonyle, benzyle ou
    Figure imgb0139
    R₁₆   est de l'hydrogène,
    R₁₇   est de l'hydrogène ou un groupe méthyle,
    R₁₈   est un groupe (alkyle en C₁ à C₄)carbonyle, aminocarbonyle,
    R₁₉   est de l'hydrogène ou un groupe alkyle en C₁ à C₁₀,
    X   est une liaison directe ou un groupe alkylène en C₂ à C₄ et
    m   a la valeur 0 ou 1.
  3. Matériau photosensible contenant un halogénure d'argent suivant la revendication 1, caractérisé en ce qu'on utilise par mole d'halogénure d'argent 10⁻⁵ à 10⁻² mole de la classe de composés A, 10⁻⁵ à 10⁻² mole de la classe de composés B, 10⁻⁶ à 10⁻³ mole de la classe de composés C et 10⁻⁶ à 10⁻³ mole de la classe de composés D.
  4. Matériau photosensible à l'halogénure d'argent suivant la revendication 1, caractérisé en ce qu'il est un matériau à l'halogénure d'argent pour la photographie en couleur comprenant un support, au moins une couche sensible au rouge, à laquelle est associé un copulant cyan, au moins une couche sensible au vert, à laquelle est associé un copulant magenta et au moins une couche sensible au bleu, à laquelle est associé un copulant jaune.
EP89120323A 1988-11-15 1989-11-03 Matériau d'enregistrement photosensible à l'halogénure d'argent Expired - Lifetime EP0373339B1 (fr)

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JP2812746B2 (ja) 1998-10-22
JPH02181744A (ja) 1990-07-16
DE58907613D1 (de) 1994-06-09
EP0373339A1 (fr) 1990-06-20
US5089381A (en) 1992-02-18

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