Classifications

• • 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
  • G03C7/3885—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 solvent

Definitions

• the invention relates to a photographic recording material with at least one silver halide emulsion layer, which contains novel light stabilizers for the image dyes produced during chromogenic development, in particular for yellow azomethine dyes.
• These dyes are said to have high color stability, with particular emphasis being placed on ensuring that the color stability of all three colors is as good as possible, so that there is no color distortion in the event of a slight fading.
• the invention is based on the object of specifying novel light stabilizers for photographic recording materials, in particular those which are suitable for improving the light stability of the yellow image dyes produced from yellow couplers.
• L1 and L2 are optionally substituted alkylene chains with 2 to 8, preferably 2 to 4 C atoms and n, m numbers from 1 to 20, preferably 1 to 5 and particularly preferably 1 to 3.
• Suitable bridge members R1 are e.g. Alkylene, cycloalkylene, alkylidene or sulfonyl groups and heteroatoms such as 0 and S.
• R2, R3 are methyl, ethyl, propyl, n-butyl, t-butyl, sec-butyl, cyclohexyl, dodecyl, hexadecyl and benzyl.
• Preferred compounds of the formula (II) correspond to the formulas wherein R12, R13 are H or alkyl.
• L1 and L2 of formula (II) are optionally substituted alkylene chains having 2 to 8, preferably 2 to 4 carbon atoms and n, m 0 to 20, preferably 1 to 5 and particularly preferably 1 to 3.
• R5 and R6 of the formulas II-A to II-C mean:
• alkyl alkyl, aryl, acyl, sulfonylamino, acylamino, ureido, alkoxy, alkoxycarbonylamino.
• the compounds according to the invention can be prepared in a simple manner by reacting OH-functional compounds of the formula III or IV (starting compound 1) with polymeric mono-, di- or polyisocyanates (starting compound 2).
• Suitable polymeric isocyanates are polymers containing isocyanate groups, which are obtained by reacting compounds with active hydrogen atoms and di- or polyisocyanates.
• the compounds with active hydrogen atoms are essentially linear and have one Molecular weight of about 300 to 10,000, preferably 500 to 4,000.
• the compounds known per se have terminal hydroxyl and / or amino groups.
• Polyhydroxyl compounds such as polyesters, polyacetals, polyethers, polyamides, polyesteramides and polycarbonates are preferred. The hydroxyl number of these compounds therefore corresponds to about 370 to 10, in particular 225 to 28.
• polyethers e.g. the polymerization products of ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide and their mixed or graft polymerization products, as well as the condensates obtained by condensation of polyhydric alcohols or mixtures thereof and the products obtained by alkoxylation of polyhydric alcohols.
• polyacetals e.g. the compounds that can be prepared from hexanediol and formaldehyde are questionable.
• the predominantly linear condensates obtained from polyvalent saturated or unsaturated carboxylic acids and polyvalent saturated alcohols, amino alcohols, diamines and their mixtures are suitable as polyesters, polyester amides and polyamides.
• Polyhydroxyl compounds already containing urethane or urea groups can also be used.
• Mixtures of different polyhydroxyl compounds can of course be used to vary the lyophilicity or the hydrophobicity and the mechanical properties of the process products.
• Suitable polyisocyanates for the preparation of the polymers containing NCO groups are all aromatic and aliphatic diisocyanates or triisocyanates such as, for example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, 4,4 ' -Dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, the isomers of tolylene diisocyanate, optionally in a mixture, preferably the aliphatic diisocyanates, butane-1,4-diisocyanate, hexane-1,6-diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1 , 4-diis
• the NCO prepolymers can be prepared in accordance with the regulations mentioned in Houben-Weyl, volume 205, p. 1613 ff (Georg Thieme Verlag, Stuttgart, New York, 1987).
• the NCO prepolymers or the polymers produced by polycondensation preferably contain in their chain urethane groups and / or urea groups which were formed during the reaction of the compounds containing active hydrogen atoms with polyisocyanates.
• the compounds are preferably used in an amount of 0.1 to 4 g / g of color coupler, in particular in an amount of 0.4 to 1 g / g of color coupler.
• the compounds can be used in combination with other dye stabilizers.
• the color photographic recording material according to the invention contains at least one light-sensitive silver halide emulsion layer and preferably a sequence of several such light-sensitive silver halide emulsion layers and optionally further auxiliary layers such as, in particular, protective layers and non-light-sensitive binder layers arranged between the light-sensitive layers, wherein according to the present invention at least one of the light-sensitive silver halide emulsion layers present is associated with a compound according to the invention in combination with a color coupler, preferably a yellow coupler.
• the compounds according to the invention act primarily as light stabilizers, i.e. the dyes formed from the color coupler during chromogenic development, as a rule azomethine dyes, have a considerably increased stability to the action of light in the presence of the compounds according to the invention. Furthermore, the compounds according to the invention also improve the stability of the dye against the action of moisture and heat. In addition, the compounds according to the invention also take on the function of an oil former for the color coupler, i.e. they can be used either alone or together with other known oil formers as coupler solvents. In the latter case, the compounds according to the invention preferably make up at least 50% by weight of the total amount of oil former in the respective layer. The fact that further oil formers are not required has a favorable effect on the layer loading and / or the total layer thickness of the recording materials according to the invention.
• the compounds according to the invention fall mostly during the preparation (reaction of the compounds containing active hydrogen atoms with polyisocyanates) as a solution in aprotic (hydrophobic) solvents, e.g. Ethyl acetate, and can be used in the form of this solution directly during incorporation into the casting solution for the layer in question, optionally together with the respective color coupler.
• aprotic (hydrophobic) solvents e.g. Ethyl acetate
• the incorporation is carried out in the customary manner, it being possible, if appropriate, to use further auxiliary solvents and / or high-boiling coupler solvents, so-called oil formers, but the latter preferably in a minor amount.
• 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. 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 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, e.g.
• Platelet-shaped crystals can 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.
• AgBrCl emulsions with at least 80 mol% AgCl, in particular at least 95 mol% AgCl, are preferably used.
• 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.
• 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 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).
• Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (for example gold, platinum, palladium, iridium).
• Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic compounds can also be used Nitrogen compounds (eg imidazoles, azaindenes) or spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds ", 1964, or Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Vol. 18, pp. 431 ff. And Research Disclosure 17643 (Dec. 1978), Chapter III).
• a reduction sensitization can be added under Adding reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidinesulfinic acid) can be carried out by hydrogen, by low pAg (eg less than 5) and / or high pH (eg above 8).
• the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
• Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. 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, optionally substituted benzotriazoles or benzothiazolium salts can be used as antifoggants.
• metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can be used as antifoggants.
• Heterocycles containing mercapto groups for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
• mercaptobenzthiazoles for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines
• 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.).
• 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, glycerin compounds or glycidol compounds
• cationic surfactants e.g.
• alkyl amines quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.
• an acid group e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group
• ampholytic surfactants e.g. 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.
• cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.
• 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, for example ⁇ -pivaloylacetanilide couplers.
• Preferred yellow couplers are 2-equivalent- ⁇ -pivaloylacetanilide couplers; whose leaving group is linked to the coupling position via oxygen or nitrogen.
• Suitable yellow couplers include the following:
• 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 which are colorless, as well as those which have an intensive intrinsic color which disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers which, when reacted with color developer oxidation products, essentially give 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.
• DIR couplers the development inhibitors of the azole type, e.g. Triazoles and benzotriazoles release 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 into essentially photographically ineffective products in the developer bath are described, 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 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-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 Suitable for FAR couplers which give essentially colorless products when 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-O 043 037.
• oligomers or polymers instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
• the compounds according to the invention are used in particular for the yellow-coupling layer.
• 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 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.
• 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), 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 UV-absorbing compounds; White toners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D Min dyes, additives to improve dye, coupler and white stabilization and to reduce the color haze, plasticizers (latices), biocides and others contain.
• Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or benzoxazole compounds (US-A-3,700,455).
• binder layers in particular the 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.
• Additives to improve dye, coupler and whiteness stability and to reduce the color fog can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromans, spiroindanes , p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
• Examples of particularly suitable compounds are: Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading due to UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus the color rendering to improve a film. Connections of different structures are usually used for the two tasks.
• Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or benzoxazole compounds (US-A-3,700,455).
• the following two layers were applied to a paper coated on both sides with polyethylene.
• the quantities relate to one m2.
• Blue-sensitive silver halide emulsion layer made of 0.6 g AgNO3 (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.78 ⁇ m) 2 g gelatin 0.8 g yellow coupler Y-9 0.6 g tricresyl phosphate (CPM)
• Samples 2 to 5 were prepared in the same manner as sample 1, with the difference that the CPM used in sample 1 was replaced by one of the compounds according to the invention, as indicated in table 1, in the same amount.
• the samples were then exposed behind a graduated gray wedge.
• the materials were then processed in the customary manner using the processing baths listed below.
• Ethylenediaminetetraacetic acid di-Na salt 2.2 g / l Potassium chloride 2.5 g / l 1,2-Dihydroxybenzene-3,4,6-trisulfonic acid trisodium salt make up to 1,000 ml with water; pH 10.0 0.3 g / l
• the processed samples are then covered with a UV protective film and irradiated in a xenon test device to determine the light fastness (20 ⁇ 106 lx h).
• the UV protective film was produced as follows: A layer of 1.5 g of gelatin, 0.65 g of compound A (UV absorber) of the following formula was applied to a transparent cellulose triacetate film provided with an adhesive layer 0.07 g dioctyl hydroquinone and 0.36 g tricresyl phosphate applied. The quantities refer to 1 m2. Table 1 sample Oil generator / polymer Density decrease in% at density 1.0 D max 1 comparison CPM 40 65 2nd erf. II-14 23 43 3rd erf. I-2 17th 30th 4th erf. I-1 18th 29 5 erf. II-17 20th 41
• Table 1 shows that the light stability of the dye is significantly improved by the compound according to the invention.
• Example 1 was repeated with the change that the yellow coupler Y-21 was used in the same amount instead of the yellow coupler Y-9.
• the comparative compound P-1 was used in the same amount instead of a compound according to the invention:
• R4 polyester from adipic acid and butanediol
• the processed samples were subjected to a Xenotest as described in Example 1. The results are shown in Table 2.
• the example shows that the light stability of the image dyes is improved by using the compounds according to the invention.
• the polymer P-1 according to EP-542 053 used as a comparison also brings about an improvement in the light stability, but the samples show a significantly higher coloration of the image whites (A) and a disadvantageously higher coloration of the image whites (B) after storage in a climatic chamber (table 3).
• 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.
• the layer structure in the 2nd layer replaced TKP with the same amount by weight of a polymer according to the invention.
• the processed material was further stored in a climatic oven (80 ° C, 50% relative humidity, 21 days), whereby the yellow dye is shown in the table below decomposed into colored products.
• the densities behind red and green filters before and after storage in a climatic cabinet (at density 2.0 behind blue filters before storage) were determined with a hand densitometer. The percent density increases are given in Table 5.
• Table 5 sample Polymer / oil former Additional density in% at Yellow output density 2.0 measured behind the green filter Yellow output density 2.0 measured behind the red filter 17th comparison CPM 15 43 18th erf. II-14 10th 29 19th erf. I-2 8th 31 20th erf. I-1 10th 27 21 comparison P-1 11 32

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• 1993
  • 1993-11-08 DE DE4338105A patent/DE4338105A1/de not_active Withdrawn
• 1994
  • 1994-10-26 EP EP94116953A patent/EP0652475A1/fr not_active Withdrawn
  • 1994-10-27 US US08/329,886 patent/US5441862A/en not_active Expired - Fee Related
  • 1994-11-04 JP JP6293628A patent/JPH07191442A/ja active Pending

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