EP0585672B1 - Matériau d'enregistrement photographique - Google Patents

Matériau d'enregistrement photographique Download PDF

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Publication number
EP0585672B1
EP0585672B1 EP93112875A EP93112875A EP0585672B1 EP 0585672 B1 EP0585672 B1 EP 0585672B1 EP 93112875 A EP93112875 A EP 93112875A EP 93112875 A EP93112875 A EP 93112875A EP 0585672 B1 EP0585672 B1 EP 0585672B1
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EP
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Prior art keywords
layer
compounds
color
alkyl
photographic
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EP93112875A
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German (de)
English (en)
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EP0585672A2 (fr
EP0585672A3 (en
Inventor
Markus Dr. Geiger
Hans-Horst Dr. Steinbach
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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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/151—Matting or other surface reflectivity altering material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/152—Making camera copy, e.g. mechanical negative

Definitions

  • the invention relates to a photographic recording material with improved surface properties.
  • Photographic recording materials usually consist of a support on which at least one photosensitive silver halide emulsion layer and at least one protective layer are applied.
  • Gelatin which is hardened with a suitable hardening agent, is usually used as the binder for the silver halide grains, so that the photographic materials can also be processed at temperatures above 30 ° C. after exposure.
  • the photographic materials are usually available as rolls or as a single sheet stack. In both cases, it is required that the static friction and the sliding friction coefficient have an optimal value, which should be the same before and after processing, if possible. If these coefficients are too low, that is, if the lubricity is too high, no exact ones can be made Stacks are formed; the individual leaves slide away from each other. Correspondingly, rolls do not form flush edges, which leads to problems in the foundry after drying, in assembly, when used in development machines, cameras, etc. If these coefficients are too high, the sheets adhere to one another too strongly, or, in the case of rolls, excessive forces have to be applied to unroll, which leads to static discharges and flashing, tears in the material and defects in the transport mechanisms of developing machines or cameras.
  • lubricants are usually added to the outermost layers of a photographic material, e.g. Dialkyl silicones or paraffins. With these products, improved static and sliding friction coefficients are achieved, but they do not remain sufficiently constant in processing.
  • the object of the invention was therefore to provide a photographic material which has optimally set static friction and sliding friction coefficients which, at most, change only slightly as a result of the processing.
  • Stiction is the friction that has to be overcome to move the material from the rest position to the Bring sliding, under sliding friction, the friction during sliding.
  • the invention therefore relates to a photographic recording material which contains a support and thereon at least one light-sensitive silver halide emulsion layer and a protective layer over the light-sensitive layer and optionally a back layer, the protective layer and / or back layer containing gelatin, characterized in that the gelatin-containing protective layer and / or the gelatin-containing back layer contains a silicone oil of the formula I and is hardened.
  • the silicone oil is preferably used in the protective layer over the at least one light-sensitive layer.
  • This protective layer contains in particular 0.2 to 2 g of gelatin per m2.
  • the silicone oil is used in particular in an amount of 1 to 100 mg / m2, preferably 2 to 20 mg / m2.
  • All common hardening agents can be used, eg triazine hardeners, vinyl sulfone hardeners, but especially so-called instant hardeners.
  • the coefficient of sliding friction is determined as follows:
  • the measurement is performed in accordance with DIN 53 375.
  • the sliding friction force is the force that remains effective immediately after overcoming the static friction at the specified sliding speed of 10 mm / s over a distance of 135 mm with a contact time up to the start of the measurement of 10 s.
  • the sliding friction coefficient is calculated from the sliding friction force and the normal force.
  • the sliding friction coefficient should be between 0.3 and 0.4 before and after processing the material.
  • the static friction coefficient is determined analogously to the measurement of the sliding friction coefficient and is the initial value of the measurement.
  • the measurements are dust-free in a clean room at 23 ° C and 55% rel. Humidity.
  • the coefficient of static friction should also be between 0.3 and 0.4 before and after processing.
  • Suitable compounds of formula I are, for example
  • the silicone oil can be applied together with the gelatin of the protective layer.
  • a gelatin layer can also first be cast and the silicone oil, optionally together with the hardener solution, can be applied to it.
  • the silicone oils are particularly applied in the form of an aqueous emulsion, such an emulsion e.g. consists of 35 wt .-% silicone oil, 3 wt .-% emulsifier and 62 wt .-% water.
  • Suitable emulsifiers are anionic (e.g. sodium lauryl sulfate), non-ionic (e.g. octyl polyglycol ether) or cationic (e.g. cetylammonium bromide) emulsifiers.
  • the dry scratch resistance is determined by passing a diamond with an angle of the diamond tip of 90 ° and a radius of the diamond tip of 76 »m over the surface of the material with increasing contact force. The contact force is given at the first visible layer injury.
  • the photographic material can be a black and white or color 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, for example, films and foils of semisynthetic 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 (eg 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. Oxidized gelatin can also be used. The production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff.
  • the gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
  • the 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 be 0 to 15 mol% of iodide, consist of 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 doping of the individual grain areas, being 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, for example silver benzotriazolate or silver behenate.
  • Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
  • Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe can also be present during the precipitation of the silver halides and / or the 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 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 compounds are described, for example, by Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Furthermore, salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, may be substituted as antifoggants Benzotriazoles or benzthiazolium salts are used.
  • 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
  • mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
  • Other suitable compounds are published in Research Disclosure 17643 (Dec. 1978), Chapter VI.
  • 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 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.
  • 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 become cyan couplers, assigned to the green-sensitive layers of purple couplers and the blue-sensitive layers of yellow couplers.
  • Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type.
  • Color couplers for generating the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type.
  • Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the ⁇ -acylacetamide type; suitable examples are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers.
  • the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
  • the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, 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 couplers that are listed in the Coupling point contain a cleavable residue that is released upon reaction with color developer oxidation products and thereby either directly or after one or more other groups have been cleaved from the primary cleaved residue (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), exhibits a certain desired photographic activity, 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.
  • DIR couplers the development inhibitors of the azole type, e.g. Release triazoles and benzotriazoles are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281.28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416.
  • Other advantages for color rendering, i.e. Color separation and color purity, and for detail reproduction, i.e. Sharpness and graininess can be achieved with such DIR couplers, e.g. do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further subsequent reaction, which is achieved, for example, with a timing group.
  • DIR couplers which release a development inhibitor which is decomposed in the developer bath into essentially photographically ineffective products are, for example in DE-A-32 09 486 and in EP-A-0 167 168 and 0 219 713. 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, e.g. also light-insensitive or intermediate layers. However, they are preferably added to the photosensitive silver halide emulsion layers, the characteristics of the silver halide emulsion, e.g. whose iodide content, the structure of the silver halide grains or their grain size distribution influence 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 a color in the coupling in the respective layer in which it is introduced, which color differs from the color to be produced in this layer.
  • DAR or FAR couplers in particular can be used can be used that 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-0 089 834, 0 110 511, 0 118 087 , 0 147 765 and in U.S.-A-4,618,572 and 4,656,123.
  • 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 liberate, for example, 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 Pat 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 liberate, for example, 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 Pat US-A-4 636 546, 4 345 024, 4 684 60
  • 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 from the compound in question and then adding it to the casting solution for the layer in question.
  • the selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
  • Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-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 e.g. dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers are, for example, alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
  • oil formers 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-t-amylphenol, dioctyl azate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-octoxy-5-butyl-2-
  • 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 by dispensing with the yellow filter layer, in which, for example, the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow the support.
  • 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), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP A-0 069 070, 0 098 072, 0 124 877, 0 125 522.
  • sub-layers of the same spectral sensitization can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains.
  • the sublayer with higher sensitivity will be located further away 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, e.g. separated by layers of other spectral sensitization.
  • 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 compounds that absorb UV light, white toners, spacers, Filter dyes, formalin scavengers, light stabilizers, antioxidants, D Min dyes, additives to improve the dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), 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 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).
  • the protective layer according to the invention preferably contains such spacers, in particular in an amount of 2 to 10 mg / m 2.
  • the average particle diameter of the spacers is in particular in the range from 0.2 to 10 »m, preferably in the range from 0.7 to 2.5» m.
  • the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath.
  • suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
  • Additives to improve dye, coupler and whiteness stability and to reduce the color haze can belong to the following chemical classes of substances: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes, p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified metal complexes or etherified phenyl complexes or ether groups .
  • 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-A-2 586
  • 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, preferably after being poured on, at the latest after 24 hours after 8 hours at the latest the hardening is completed to such an extent that no further change in the sensitometry and the swelling of the layer structure caused by the crosslinking reaction occurs.
  • Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
  • hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.
  • the instant hardeners are preferably used in an amount of 0.1 to 3.0 g / m2.
  • 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 in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound to react.
  • 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.
  • 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.
  • Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used as bleaching agents.
  • Iron (III) complexes of aminopolycarboxylic acids in particular, for example, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids are particularly preferred.
  • Persulphates and peroxides for example hydrogen peroxide, are also suitable as bleaching agents.
  • 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.
  • a color photographic recording material was produced by applying the following layers in the order given on a paper coated on both sides with polyethylene.
  • the quantities given relate to 1 m2.
  • the corresponding amounts of AgNO3 are given.
  • Examples 5 to 8 according to the invention provide constant values for GK, HK and TKF before and after processing, while the comparative tests are either too poor or, if the value is good before processing, deteriorate considerably as a result of processing.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (7)

  1. Matériau d'enregistrement photographique, qui contient un support et sur celui-ci au moins une couche photosensible d'émulsion aux halogénures d'argent et une couche protectrice sur la couche photosensible et éventuellement une couche dorsale, dans lequel la couche protectrice et/ou la couche dorsale contiennent de la gélatine, caractérisé en ce que la couche protectrice contenant de la gélatine et/ou la couche dorsale contenant de la gélatine contiennent une huile de silicone de formule I
    Figure imgb0026
     dans laquelle
    R₁   est un groupe hydroxy, alcoxy, cycloalcoxy ou aryloxy,
    R₂   est un reste de formule
    Figure imgb0027
     ou R₁,
    R₃ et R₄   sont chacun un groupe alkyle, aryle ou cycloalkyle,
    R₅ et R₆   sont chacun H ou un groupe alkyle, aminoalkyle ou polyaminoalkyle,
    A   est un reste alkylène à chaîne droite ou ramifiée en C₃-C₂₀, avec une chaîne carbonée en au moins C₃ entre l'atome Si et l'atome N
    m   est un nombre de 10 à 1 000 et
    p   est un nombre de 1 à 350,
    et ladite couche est durcie.
  2. Matériau photographique selon la revendication 1, caractérisé en ce que l'huile de silicone de formule I est introduite dans la couche protectrice sur la ou les couches photosensibles.
  3. Matériau photographique selon la revendication 2, caractérisé en ce que la couche protectrice contient 0,2 à 2 g de gélatine/m² et 1 à 100 mg d'huile de silicone/m².
  4. Matériau photographique selon la revendication 1, caractérisé en ce que
    R₁   est un groupe alcoxy en C₁-C₄
    R₂   est un groupe alcoxy en C₁-C₄ ou un reste de formule
    Figure imgb0028
    R₃ et R₄   sont chacun un groupe alkyle en C₁-C₄
    R₅ et R₆   sont chacun un atome d'hydrogène ou un groupe ou un groupe alkyle en C₁-C₄, cyclohexyle ou phényle, un reste -CH₂-CH₂-NH₂ ou un reste -(CH₂-CH₂-NH))q-CH₂-CH₂-NH₂
    A   est un reste -(-CH₂-CH₂)n-
    m   est un nombre de 50 à 200
    n   est un nombre de 3 à 8
    p   est un nombre de 30 à 150 et
    q   est un nombre de 1 à 8.
  5. Matériau photographique selon la revendication 1, caractérisé en ce que la couche protectrice et/ou la couche dorsale contiennent des particules inertes organiques ou inorganiques.
  6. Matériau photographique selon la revendication 5, caractérisé en ce que les particules inertes ont un diamètre moyen de particules de 0,7 à 2,5 »m et sont utilisées en quantité de 1 à 10 mg/m².
  7. Matériau photographique selon la revendication 1, caractérisé en ce que le durcissement est effectué avec un durcisseur instantané.
EP93112875A 1992-08-24 1993-08-11 Matériau d'enregistrement photographique Expired - Lifetime EP0585672B1 (fr)

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DE4228003 1992-08-24

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EP0585672A3 EP0585672A3 (en) 1994-07-13
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US5575407A (en) * 1990-10-25 1996-11-19 Contico International, Inc. Low cost trigger sprayer having container with integral saddle
US5451495A (en) * 1994-08-15 1995-09-19 Eastman Kodak Company Recording element having a crosslinked polymeric layer
US5723271A (en) * 1996-11-19 1998-03-03 Eastman Kodak Company Photographic elements having a process-surviving polysiloxane block copolymer backing
US5723270A (en) * 1996-11-19 1998-03-03 Eastman Kodak Company Photographic elements having a process-surviving polysiloxane block copolymer backing
EP0911695A1 (fr) * 1997-10-20 1999-04-28 Eastman Kodak Company Compositions de revêtement aqueuses pour couches protectrices superficielles d'éléments formant image
DE19850363A1 (de) 1998-11-02 2000-05-04 Basf Ag Polymere für kosmetische Formulierungen
GB0329925D0 (en) 2003-12-24 2004-01-28 Eastman Kodak Co Imaging element having improved durability
US7153636B1 (en) * 2005-08-01 2006-12-26 Eastman Kodak Company Thermally developable materials with abrasion-resistant backside coatings
JP4551944B2 (ja) * 2007-05-15 2010-09-29 利春 深井 油分乳化物

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US4109449A (en) * 1976-06-23 1978-08-29 Gibson Otto L Fruit picking apparatus
IT1129033B (it) * 1980-09-17 1986-06-04 Minnesota Mining & Mfg Elementi fotografici a colori aventi migliorare proprieta' meccaniche
JPS6142653A (ja) * 1984-08-07 1986-03-01 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPH04127142A (ja) * 1990-06-22 1992-04-28 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
US5208139A (en) * 1990-12-11 1993-05-04 Fuji Photo Film Co., Ltd. Silver halide photographic materials
JP2802684B2 (ja) * 1990-12-11 1998-09-24 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JP2927370B2 (ja) * 1991-01-04 1999-07-28 コニカ株式会社 ハロゲン化銀写真感光材料

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EP0585672A2 (fr) 1994-03-09
EP0585672A3 (en) 1994-07-13

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