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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
• • 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
  • Y10S430/162—Protective or antiabrasion layer

Definitions

• the invention relates to a photographic recording material with a support, at least one light-sensitive silver halide emulsion layer, a protective layer and optionally further layers, which exhibits improved properties, in particular an improved maximum density.
• the object of the present invention was to provide photographic recording materials with improved properties, in particular improved maximum densities.
• the photographic silver halide recording material contains in at least one layer which is arranged closer to the support than the protective layer, a compound which corresponds in the form of the free acid to the following formula wherein R1 alkylene, arylene, aralkylene or cycloalkylene, L the rest of a polyester diol with an average molecular weight of 500 to 20,000, m 0 or 1, n 0 to 30, preferably 0 to 10 and m + n ⁇ 1 mean.
• polyester carboxylic acids according to the invention have a block-like structure; hydrophobic polyester blocks with a molecular weight of ⁇ 500 alternate with hydrophilic blocks which carry two free carboxyl groups.
• polyester carboxylic acids according to the invention preferably have acid numbers of 30 to 340 mg KOH / g, in particular 50 to 200 mg KOH / g.
• the compounds of the formula I are used in acid form in particular as oil formers and in anionic form as surfactants and emulsifiers.
• oil formers they are preferably used in an amount of 0.02 to 5.0 g / m2, particularly preferably 0.2 to 3 g / m2, and as surfactants preferably in an amount of 0.01 to 3.0 g / m2 preferably 0.05 to 2 g / m2 used.
• the compounds according to the invention can be used as oil formers in all layers in which layer components are used in emulsified form. The same applies to use as a surfactant.
• the compounds according to the invention can take on both oil formers and emulsifiers.
• the compounds of the formula I are prepared by reacting polyester diols of the formula II with carboxylic anhydrides of the formula III or corresponding di- and tetracarboxylic acids at from 20 to 200 ° C. in a molar ratio of 1: 1 to 1: 2, if appropriate in inert solvents:
• the condensation reaction is preferably carried out without solvent, in particular at temperatures from 50 to 150 ° C.
• the compounds of the formula I When used as emulsifiers, the compounds of the formula I are neutralized in an aqueous medium with alkali metal hydroxides or amines. Suitable cations are Na+, K+, Li+, ammonium, mono-, di-, tri- or tetraalkylammonium and di- or tri-hydroxyalkylammonium.
• the alkyl groups have in particular one to four carbon atoms.
• the polyester diols II are known, for example, from Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 19, p. 305 ff. They are produced by polycondensation of one or more diols with one or more dicarboxylic acids and / or one or more oxy acids. Diols and dicarboxylic acids are preferably used. The oxyacids can be used as lactones.
• diols examples include polyalkylene glycols in which the alkylene group has 2 to 4 carbon atoms, such as diethylene glycol, triethylene glycol, polyethylene glycol (average molecular weight about 200 to 1,000), 1,2-propylene glycol, 1,3-propylene glycol, polypropylene glycol (average molecular weight about 170 to 1,000), or diols of the general formula HO-R2-OH in the R2 is a divalent hydrocarbon group containing 2 to 13 carbon atoms, such as straight-chain or branched alkylene groups or cycloalkylene groups (such as ethylene, propylene, butylene, isobutylene, pentylene, neopentylene, octylene, tridecylene and cyclohexylene groups), and those groups which are substituted by one or more alkoxy groups with 1 up to 4 carbon atoms (such as ethoxy or propoxy groups), phenyl groups, which can be substituted with one or
• Ethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol are preferred.
• Preferred dicarboxylic acids are succinic acid, adipic acid, phthalic acid, sebacic acid, dodecanedicarboxylic acid.
• the lactone of an oxycarboxylic acid is e.g. Caprolactone into consideration.
• the average molecular weight, determined from the OH number by the end group method, of the polyester diols of the formula (II) is about 500 to 20,000, preferably 800 to 5,000.
• the molar ratio of polyhydric alcohol to polybasic carboxylic acid is greater than 1. Examples of polyester diols are listed in Table 1.
• Polyester diols (II) Polyester diol Dicarboxylic acid Diol middle Molecular weight OH number II-1 Adipic acid 1,4-butanediol 1,500 75 II-2 Adipic acid Neopentyl glycol 1,700 66 II-3 Succinic acid Ethylene glycol 2,000 56 II-4 Adipic acid Propylene glycol 1,200 93 II-5 Sebacic acid Ethylene glycol 3,500 32 II-6 Dodecanedicarboxylic acid Ethylene glycol 1,900 59 II-7 Succinic acid Hexanediol 800 140 II-8 Adipic acid Diethylene glycol 2,400 46 II-9 Succinic acid Neopentyl glycol 4,200 27th II-10 Adipic acid 1,4-butanediol / neopentyl glycol 50:50 * 3,200 35 II-11 Adipic acid / phthalic acid 50:50 * Ethylene glycol 2,000 56 II-12 Adipic acid 1,4-butanediol
• Carboxylic anhydrides of the formula (III) are, for example
• polyester carboxylic acids according to the invention are soluble in ethyl acetate. As carboxylates, they are soluble in water or form colloidal solutions with an average particle size of up to 100 nm.
• the polyester emulsifiers of the general formula (I) are particularly suitable as emulsifiers in aqueous emulsion polymerization for the preparation of latices useful for photography. They deteriorate the properties of the latices to a much lesser extent than the usual emulsifiers. Since, in contrast to these, they are relatively high molecular weight and show good polymer compatibility, they can also be obtained from multiphase systems, e.g. B. Mixtures with binders, do not so easily sweat out, the transparency of the coatings with these mixtures is improved.
• polyester diols which are known to the person skilled in the art as soft segments, are used in polymer emulsifiers of the formula (I).
• Polyester diols which are used as soft segments, contain, in addition to 1,6-hexanediol, preferably neopentyl glycol and / or ⁇ -hydroxyethylhexanediol as the diol and adipic acid as the dicarboxylic acid.
• Caprolactone diols are also known as soft segments. (Angew. Makromol. Chem. 14 , 75 (1970) and 16/17, 117 (1971)).
• the usual monomers such as acrylic esters, methacrylic esters, vinyl esters, vinyl aromatics, conjugated dienes, vinyl halides, (meth) acrylonitrile, divinyl compounds and / or (meth) allyl compounds, but in particular monomers with photographically useful groups, can be used for the polymerization in the presence of the emulsifiers according to the invention .
• water-soluble monomers such as, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, styrenesulfonic acid, methallylsulfonic acid, acrylamido-2-methylpropanesulfonic acid, acrylamide can be added in amounts of up to 20%, if necessary, to improve the stability of the polymer latices against electrolyte additives Polymers are installed.
• Photographically useful groups are, for example, pp, gb, bg color couplers, white couplers, DIR couplers, UV absorbers, optical brighteners, mask couplers, filter dyes.
• polyester diol II-2 from adipic acid and neopentyl glycol with an average molecular weight of 1,700 and 2.18 g of benzene-1,2,4,5-tetracarboxylic acid (96% by weight) are mixed, 4 hours to 160 ° C heated with stirring and the water formed was distilled off. After cooling, a clear, homogeneous polyester carboxylic acid with an acid number of 73 mg KOH / g is obtained.
• polyester diol II-2 and 4.36 benzene-1,2,4,5-tetracarboxylic acid 96% by weight are mixed, heated to 160 ° C. for 5 hours with stirring and the water formed is distilled off. After cooling, a clear, homogeneous polyester carboxylic acid with an acid number of 144 mg KOH / g is obtained.
• polyester carboxylic acids according to Table 2 are obtained by reacting polyester diols II with carboxylic anhydrides.
• Table 2 Polyester carboxylic acid Polyester diol Carboxylic anhydride Molar ratio of polyester diol / carboxylic anhydride Acid number I-4 II-1 III-2 1: 1.5 122 I-5 II-1 III-5 1: 1 65 I-6 II-2 III-6 1: 1 58 I-7 II-4 III-5 1: 1.5 146 I-8 II-7 III-8 1: 1 110 I-9 II-9 III-7 1: 2 72 I-10 II-10 III-12 1: 2 92 I-11 II-10 III-8 1: 2 98 I-12 II-6 III-10 1: 2 150 I-13 II-2 III-5 1: 2 156
• 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 supports can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light.
• the surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.
• the color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.
• Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.
• Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers.
• Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrolidone, 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.
• the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
• functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
• the gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used. The production such gelatins are described, for example, in The Science and Technology of Gelatine, edited by AG Ward and A. Courts, Academic Press 1977, page 295 ff.
• the gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
• the silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide.
• the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide.
• silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions are usually used.
• the crystals can be predominantly compact, which are, for example, regularly cubic or octahedral or can have transitional forms.
• platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
• the layers can also have tabular silver halide crystals, where the ratio of diameter to thickness is significantly greater than 5: 1, e.g. 12: 1 to 30: 1.
• the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different.
• the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be both homo- and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%.
• the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.
• Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
• the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
• various methods e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
• the silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used.
• the latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide.
• the water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded.
• the pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation.
• so-called inverse precipitation with an excess of silver ions is also possible.
• the silver halide crystals can also grow through physical ripening (Ostwald ripening), in the presence of excess halide and / or silver halide complexing agent. The growth of the emulsion grains can even take place predominantly by Ostwald ripening, a fine-grained, so-called Lippmann emulsion preferably being mixed with a less soluble emulsion and being redissolved on the latter.
• Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe can also be present during the precipitation and / or physical ripening of the silver halide grains.
• the precipitation can also be carried out in the presence of sensitizing dyes.
• Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.
• the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration 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. with H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).
• Iridium and rhodium take place, furthermore thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic nitrogen compounds (e.g. 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, p. 431 ff. and Research Disclosure No. 17643, section III) are added.
• a reduction sensitization with the addition of reducing agents can be carried out by hydrogen, by low pAg (eg less than 5) and / or high pH (eg above 8) .
• the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
• Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles can also be used as antifoggants such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzthiazolium salts.
• metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles
• antifoggants such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzthiazolium salts.
• Heterocycles containing mercapto groups for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
• mercaptobenzthiazoles for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines
• these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
• a water-solubilizing group for example a carboxyl group or sulfo group.
• the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
• the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
• the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
• 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.
• carboxylic acid for example carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, for example amino acid and aminosulfonic acid compounds and sulfuric or phosphoric acid esters of an amino alcohol, but in particular also the carboxylates according to the invention.
• the photographic emulsions can be spectrally sensitized using methine dyes or other dyes.
• Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
• 9-ethylcarbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups the can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl and 9-ethyl-naphthoxathia or -selenecarbocyanine and 9-ethyl-naphthothiaoxa- or -benzimidazocarbocyanine, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.
• red sensitizers RS examples include, in particular for negative and reversal film, the red sensitizers RS, green sensitizers GS and blue sensitizers BS listed below, which can be used individually or in combination with one another, for example RS 1 and RS 2, and GS 1 and GS 2.
• Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromides.
• the differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it.
• the red-sensitive layers usually turn blue green couplers, the green-sensitive layers of purple couplers and the blue-sensitive layers of yellow couplers.
• Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the ⁇ -acylacetamide type; suitable examples of this are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers of the formulas
• the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
• the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling.
• the 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products.
• the 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling point, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue (eg DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolds, for example as a development inhibitor or accelerator.
• Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR and FAR couplers.
• white couplers are:
• DIR couplers which release development inhibitors of the azole type, for example triazoles and benzotriazoles, are described in DE-A-2 414 006, 2 610 546, 2 659 417, 2 754 281, 2 726 180, 3 626 219, 3 630 564 3 636 824, 3,644,416 and 2,842,063. Further advantages for color rendering, that is, color separation and color purity, and for detail rendering, that is, sharpness and granularity, can be achieved with those DIR couplers which, for example, do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further follow-up reaction, which is achieved, for example, with a timing group.
• DIR couplers which release a development inhibitor which is decomposed into essentially photographically ineffective products in the developer bath are described, for example, in DE-A-32 09 486 and in EP-A-167 168 and 219 713. This measure ensures trouble-free development and processing consistency.
• the DIR couplers can be added to a wide variety of layers in a multilayer photographic material, for example also light-insensitive or intermediate layers. However, they are preferably added to the light-sensitive silver halide emulsion layers, the characteristic properties of the silver halide emulsion, for example its iodide content, the structure of the silver halide grains or their grain size distribution having an influence on the photographic properties achieved.
• the influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it may be advantageous to insert a DIR coupler set, which forms in the respective layer in which it is introduced, a color different from the color to be generated in this layer in the coupling.
• DAR or FAR couplers can be used, which release a development accelerator or an fogger.
• Compounds of this type are, for example, in DE-A-2 534 466, 3 209 110, 3 333 355, 3 410 616, 3 429 545, 3 441 823, in EP-A-89 834, 110 511, 118 087, 147 765 and described in US-A-4,618,572 and 4,656,123.
• DIR couplers examples are:
• DIR, DAR or FAR couplers Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-1 547 640).
• 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-3 145 640, 2 515 213, 2 447 079 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
• 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 polyester carboxylates according to the invention can be used as emulsifiers in their preparation.
• 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 e.g. dyes
• pickling polymers e.g. acrylic acid
• Suitable oil formers are, for example, alkyl phthalates, phosphonic esters, phosphoric esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
• oil formers examples include dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phylate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert.-amylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N,
• polyester carboxylic acids according to the invention are preferably used as oil formers, optionally in a mixture with other oil formers, the compounds according to the invention accounting for at least 50% by weight.
• 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, which in turn are closer than blue-sensitive layers there is generally a non-light-sensitive yellow filter layer between green-sensitive layers and blue-sensitive layers.
• green or red-sensitive layers are suitably low in their own sensitivity, other layer arrangements can be selected without the yellow filter layer, in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.
• the non-light-sensitive intermediate layers which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
• Suitable agents which are also called scavengers or EOP scavengers, are described in Research Disclosure 17.643 / 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.
• R1, R2 -t-C8H17 -sec-C12H25 -t-C6H13 -sec-C8H17 -C15H31
• 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 from the support than the sublayer with lower sensitivity.
• Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, for example through Separate layers of other spectral sensitization.
• all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A 1 958 709, DE-A 2 530 645, DE-A 2 622 922).
• the photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives for improving the stabilization of dyes, couplers and whites and for reducing the color fog and others.
• Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film.
• Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. Nos. 3,314,794 and 3,352,681), benzophenone compounds (JP-A 2784/71), cinnamic acid ester compounds (US Pat. Nos. 3,705,805 and 3,707) 375), butadiene compounds (US-A 4 045 229) or benzoxazole compounds (US-A 3 700 455).
• Ultraviolet absorbing couplers such as ⁇ -naphthol type cyan couplers
• ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
• Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
• Suitable white toners are e.g. in Research Disclosure December 1978, page 22 ff, Unit 17,643, 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 3 331 542, DE-A 3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter XVI).
• photographically inert particles of inorganic or organic nature e.g. as a matting agent or as a spacer (DE-A 3 331 542, DE-A 3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter XVI).
• the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
• the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath.
• suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
• Suitable formalin scavengers include
• Additives to improve dye, coupler and whiteness stability and to reduce the color fog can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes, p- Alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
• the layers of the photographic material can be hardened with the usual hardening agents.
• Suitable curing agents are, for example, formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen 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
• the hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
• Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry caused by the crosslinking reaction and the swelling of the layer structure occurs .
• Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
• hardening agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin with the formation of peptide bonds and crosslinking of the gelatin.
• Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step.
• All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound.
• Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
• Further useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.
• bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used.
• Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
• Persulphates 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 functions as a final bath.
• development is initially carried out using a black and white developer whose oxidation product is not capable of reacting with the color couplers. This is followed by a diffuse second exposure and then development with a color developer, bleaching and fixing.
• Emulgate E-1 to E-5 were mixed in various samples of a red-sensitized silver halide emulsion.
• the silver halide gelatin emulsion consisted of 75 g of silver bromide iodide (iodide content 3 mol%) and 72 g of gelatin, based on 1 kg of emulsion.
• the emulsions prepared in this way were applied to a cellulose triacetate layer support provided with an adhesive layer, dried and hardened.
• the application of silver bromide is 1.65 g / m2; the order for couplers and oil formers each 1.0 g / m2.
• the hardening is carried out by covering with a 1% by weight solution of the hardener of the formula
• Color developer Distilled water 800 g Hydroxyethane disphosphonic acid di-Na salt 2 g Ethylenediaminetetraacetic acid di-Na salt 2 g Potassium carbonate 34 g Sodium bicarbonate 1.55 g Sodium disulfite 0.28 g Sodium sulfite 3.46 g Potassium bromide 1.34 g Hydroxylamine sulfate 2.4 g N-ethyl-N- ( ⁇ -hydroxy) ethyl-4-amino-3-ethylaniline sulfate 4.7 g Distilled water up to 1,000 ml processing Processing [min] (25 ° C) Color developer 10th Stop bath 4th Intermediate watering 5 Bleach bath 5 Intermediate watering 5 Fixer 5 Final watering 10th
• the stop, bleach and fix baths are common bath compositions. A final bath free of formalin was used.
• the emulsions were introduced into a green-sensitized silver halide material, processed and hardened. 1.2 g / m2 of silver bromide and 0.85 g / m2 of coupler and oil former were applied.
• the latex couplers L 2, L 3, L 4 were produced in the same way, with the difference that in addition to the emulsifier oleyl methyl tauride 0.7 g, 1.4 g, 2.8 g of polyester carboxylic acid I-2 were used as the Na salt were.
• the latex couplers L 1 to L 4 were mixed into various samples of a green-sensitized silver halide emulsion which consisted of 75 g of silver bromide iodide (iodide content 3 mol%) and 72 g of gelatin, based on 1 kg of emulsion.
• the emulsions prepared in this way were applied to cellulose triacetate layer supports provided with an adhesive layer, dried and cured as in Example 1. 1.2 g / m2 of silver bromide and 1.7 g / m2 of latex coupler were applied.
• a 15 ⁇ m thick red-sensitized cyan emulsion layer was applied to a cellulose triacetate base with a 4 ⁇ m thick antihalation layer consisting of gelatin and black colloidal silver.
• the layer contained per m2 8.129 g gelatin 3.298 g of polyester carboxylic acid I-1 2.177 g tricresyl phosphate 7.13 g of silver bromide and 2.7 g of cyan couplers of the formula (40 vol.% Gelatin, 20 vol.% Polyester carboxylic acid I-1, based on the total solids content).
• polyester carboxylic acid I-2 and, as a comparison, polyethyl acrylate were used in further samples.
• the fragility was determined using the following apparatus.
• a film loop with the emulsion turned outwards is clamped in a parallel baking device with a load cell.
• a squeezing speed of 10 cm / s the movable jaw moves up to twice the film thickness against the fixed jaw and reverses again.
• the force-path curve is recorded electronically and automatically by an XY recorder.
• Latices were produced using the sodium salts of polyester carboxylic acids (pH 7.8) according to the invention. The preparation for latex 1 is described below.
• the latices 2-14 were prepared in an analogous manner (Table 7).
• the latices are distinguished by the fact that they tend to have comparatively little disruptive foam formation in comparison with the latices produced with conventional anionic emulsifiers. They are also very finely divided and very good with the binders used in photographic materials, e.g. Gelatin miscible, so that clear layers are obtained even when mixed with photographic casting solutions.
• Coupler monomer K substance according to Example 3 Coupler monomer W: Table 7 latex Polyester carboxylic acid Na+ salt (amount in% by weight, based on monomer) Monomer average particle size [nm] Foam Use in photographic material 1 I-2 5 Butyl acrylate 61 - Plasticizers 2nd I-2 10th Butyl acrylate 51 - Plasticizers 3rd I-2 50 Butyl acrylate 45 - Plasticizers 4th I-2 10th Methyl methacrylate 59 - Binder additive 5 I-2 50 Methyl methacrylate 25th - Binder additive 6 I-2 100 Methyl methacrylate 28 - Binder additive 7 I-3 10th Ethyl acrylate 28 - Plasticizers 8th I-1 50 Methyl methacrylate 24th - Binder additive 9 I-1 100 Methyl methacrylate 19th - Binder additive 10th I-1 10th Ethyl acrylate 53 - Plastic
• a color photographic recording material for the color negative development was prepared by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m2. For the silver halide application, the corresponding amounts of AgNO3 are given. All silver halide emulsions were stabilized per 100 g of AgNO3 with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
• red-sensitized silver chloride bromide iodide emulsion (5 mol% iodide; 2 mol% chloride; average grain diameter 0.5 ⁇ m) 2.4 g AgNO3, with 1.1 g of emulsifier E1 from Example 1 0.06 g MR-1 red mask 0.045 g DIR coupler DC-1 1.2 g gelatin
• red-sensitized silver bromide iodide emulsion (10 mol% iodide; average grain diameter 0.8 ⁇ m) from 2.9 g AgNO3, with 0.3 g of emulsifier E1 from Example 1 0.02 g of the MR-1 red mask 0.04 g of the DIR compound DC-2
• Green-sensitized silver bromide iodide emulsion (10 mol% iodide; average grain diameter 0.8 ⁇ m) from 2.7 g AgNO3, with 0.17 g purple coupler PP12 0.04 g yellow mask MY-1 1.6 g gelatin
• Silver bromide iodide emulsion (3 mol% iodide; average grain diameter 0.3 ⁇ m) from 0.95 g AgNO3, with 0.96 g yellow coupler GB 19 1.4 g gelatin
• Silver bromide iodide emulsion (8 mol% iodide; average grain diameter 0.8 ⁇ m) from 1.0 g of AgNO3 with 0.22 g yellow coupler GB 19 1.6 g gelatin
• a protective layer is applied to this structure, per m2 1 g gelatin 16 mg of wetting agent of the formula C8F17 SO3 ⁇ N (C2H5) 4 ⁇ contains.
• the dry layer thickness of this layer is approximately 1 ⁇ m.
• a hardening layer is applied to this layer, per m2 34 mg phenol 15.4 mg of wetting agent like protective layer 5.6 mg saponin and 374 mg of the curing agent according to Example 1 contains.
• the color coupler emulgates are manufactured according to the following recipes:
• a yellow coupler emulsate is produced in the same way as in recipe 7.1, except that instead of the polyester carboxylic acid, the same amount of tricresyl phosphate and an additional 0.42 g of wetting agent dodecylbenzosulfonate are used in I.
• a yellow coupler emulsifier is produced in the same way as for recipe V1.1, but instead of tri cresyl phosphate used the same amount of polyester diol II.10, a starting product for the polyester carboxylic acid.
• a purple emulsate is produced as recipe 7.2, but instead of the polyester carboxylic acid, the same amount of an oil form mixture dibutyl phthalate (DBP) / tricresyl phosphate (TKP) is 10: 1 and as a wetting agent 0.32 g of the compound of the formula emulsified in U.
• DBP dibutyl phthalate
• TKP tricresyl phosphate
• a purple coupler emulsifier is produced in the same way as for recipe V2.1, except that the same amount of polyester diol II.10 was used instead of the oil shaping mixture DBP / TKP 10: 1.
• a cyan coupler emulsifier is produced according to recipe 7.3, only the same amount of the oil shaping mixture TBP / TKP 3: 1 and 0.8 g of the wetting agent from V2.1 are added instead of the polyester carboxylic acid.
• the emulsifier is produced in the same way as for recipe V3.1, except that the same amount of polyester diol II.10 is used instead of the oil shaping mixture DBP / TKP 3: 1.
• the samples obtained were then exposed behind a graduated gray wedge.
• the papers were then processed in the following manner using the processing baths listed below: Development: 210 seconds, 33 ° C Bleaching: 50 seconds, 20 ° C Fix: 60 sec., 20 ° C Soak: 120 seconds, 20 ° C Dry.
• experimental setup I contains less wetting agent, which can diffuse into the baths and generates foam.
• polyester diols can be used as oil formers, but also do not give excellent maximum color densities in comparison with the polyester carboxylic acids.
• a large amount of wetting agent must be added so that the desired small particle size is obtained.
• the particle size is measured with the Autosizer II, manufacturer: MALVERN.
• Digestion stability is checked by letting the emulsions stand at 40 ° C. for 24 hours with stirring and then comparing the particle size before and after digestion. Result: sample average particle diameter [nm] Polydispersity Recipe 8.1 before digestion 239.5 0.053 Recipe 8.1 after digestion 255.2 0.060 VV1 400.9 0.270 VV2 429.1 0.287
• the cyan emulsified with the polyester carboxylic acid according to the invention has an outstandingly small particle size without the addition of wetting agent, which hardly changes even after 24 hours of digestion.
• the blue-green coupler emulsions produced with the oil former TKP (VV1) and with the oil former Polyesterdiol (VV2) have much coarser particles and a higher polydispersity. After digestion, the particles coarsen so much that a measurement is no longer possible.
• polyester carboxylic acid according to the invention combines both properties: good solution properties for color couplers and very good wetting agent action.

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• 1988
  • 1988-09-08 DE DE3830522A patent/DE3830522A1/de not_active Withdrawn
• 1989
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