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
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/30—Hardeners
• • 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
  • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • 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
  • G03C2200/00—Details
  • G03C2200/07—Anti-fading
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
• • 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
  • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
  • Y10S430/1055—Radiation sensitive composition or product or process of making
  • Y10S430/106—Binder containing
  • Y10S430/11—Vinyl alcohol polymer or derivative

Definitions

• the invention relates to a photographic recording material with respect to Wet scratch resistance and storage stability is improved.
• Photographic materials essentially contain gelatin as a binder.
• the Binder-containing layers are made with a crosslinking or hardening agent cross-linked to dry and wet materials as well as during processing to provide sufficient stability and strength.
• a hardening agent Formaldehyde, formaldehyde hydrates or formaldehyde releasers were previously used (US 2,739,059). After that it was shown that aldehydes are used in color materials contained color coupler was searched for new hardeners. It hardeners were then developed which do not have the disadvantages mentioned and used in modern multiple sprue systems, such as cascade and curtain casters can be. These hardeners work very quickly and are and immediate hardeners.
• the present invention relates to photographic materials these hardeners, especially instant hardeners, are hardened.
• Immediate hardeners are understood to mean compounds which are suitable binders network, preferably immediately after watering, at the latest after 24 hours after 8 hours at the latest, the hardening is so far completed that none further changes in the sensitometry caused by the crosslinking reaction and the swelling of the layer structure occurs.
• the difference between Wet film thickness and dry film thickness in the aqueous processing of Films understood (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
• the quick and instant hardeners have the disadvantage that due to their short hardening time achieved too low a wet scratch resistance and too high a swelling factor become.
• gelatin as a binder is that the Stability of the photographic material, especially the light stability, not is satisfactory.
• the object of the present invention was therefore a binder or binder additive to specify for gelatin that the hardening of the photographic layers with Allows immediate hardening and avoids the disadvantages mentioned.
• L 1 is directly attached to M. 1
• the molecular weight of the compound of formula (I) is in particular 10,000 to 500,000, preferably 20,000 to 200,000 (weight average).
• Alkyl radicals R 1 and R 2 have in particular 1 to 4 carbon atoms.
• the phenylene, arylene and aralkylene radicals L 1 and L 3 are preferably not further substituted.
• Comonomers M preferably have an acidic group, in particular a carboxyl group on.
• esters and amides of acrylic acid and their Derivatives e.g. of acrylic acid, ⁇ -chloroacrylic acid, methacrylic acid (for example Acrylamide, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, octyl methacrylate, lauryl methacrylate and methylenebisacrylamide), vinyl esters (e.g.
• vinyl acetate, vinyl propionate and vinyl laurate acyl nitrile, methacrylonitrile, aromatic vinyl compounds (for example styrene, vinyl toluene, divinylbenzene, vinyl acetophenone, Styrene sulfonic acid), itaconic acid.
• Preferred comonomers are vinyl acetate, crotonic acid, acrylic acid, methacrylic acid, Itaconic acid, maleic acid, fumaric acid, styrenesulfonic acid, acrylamido-2-methylpropanesulfonic acid, Sulfoethyl methacrylate and vinyl sulfonic acid.
• the compound of formula I is either a polymerized comonomer M with acidic groups and / or the group M 2 contains.
• l and j together represent 2 to 30 mol%.
• the CO-PVA can have a statistical distribution of the comonomers or be graft or block copolymers. In particular, they are copolymers with Polyacrylic acid blocks.
• Examples of polymers according to the invention are:
• the CO-PVA according to the invention can be used in photographic without further binders
• Materials are used as binders. But preferably Mixtures with known binders such as gelatin, polyvinyl pyrrolidone, Polyvinyl alcohol is used. Mixtures with are particularly preferred Gelatin.
• CO-PVA gelatin blends in generally a weight ratio of CO-PVA: gelatin from 90:10 to 5:95, preferably from 60:40 to 10:90.
• the PVA copolymers according to the invention can be used in all binders containing layers of photographic materials are used. As well it is possible to use the copolymer according to the invention in only one or a few Use layers. For example, by adding the CO-PVA in only one layer of the layer network to crosslink this layer more than that other.
• the CO-PVA are preferably in at least two layers of photographic material used. To the light stability of dyes too should improve, a CO-PVA layer above and a CO-PVA layer below the the layer containing the dye to be protected may be provided. It is irrelevant whether the layers containing CO-PVA contain emulsion, substrate, Intermediate or protective layers are.
• the photographic material is a pyrazoloazole compound contains as a purple coupler.
• a CO-PVA-containing one is preferred Layer above and a layer containing CO-PVA under the Pyrazoloazole coupler containing layer applied.
• the resulting stabilization of the purple dye obtained after processing can be added to the by adding special dye stabilizers Layer containing purple couplers can be improved.
• the dye stabilizers listed below are also suitable for Stabilization of the other dyes, especially for the yellow dye.
• Suitable dye stabilizers belong to the following classes St-I to St-IV:
• At least one compound of classes St-V to St-VIII is preferably added to the material according to the invention in order to reduce the color and storage veil.
• St-IV-2 S (CH 2 -CH 2 -COO-nC 14 H 29 ) 2
• Dye stabilizers are preferably used in an amount of 0.05 to 1 g / m 2 . This amount can be distributed over one or more layers.
• the synthesis of the CO-PVA can be carried out according to the methods described in the literature (e.g. US 2,739,059) known methods. For example, the introduction of the amino group a polymer having vinyl alcohol structural elements with aminoalkyl aldehyde acetal be implemented.
• the vinyl alcohol-vinylamine copolymers can be prepared by the method described in DE-33 26 187.
• such compounds are used as quick and instant hardeners understood that in the test described below a layer melting point of effect at least 95 ° C. Immediate hardeners are also sufficient at the beginning given definition.
• a coating solution is poured, the gelatin and, based on the gelatin, 1 wt .-% of the hardener contains.
• the coating is dried at pH 6.2 and 35 ° C and then immersed in a water bath, the is heated continuously from 20 ° C to 100 ° C for at least 5 minutes.
• the Temperature at which the layer runs off the base, recognizable by the Streaking is known as the melting point.
• the curing agents can be those that are incorporated into the binder, for example hydroxydichlorotriazine or divinyl sulfone hardener, or those which cause the binders to crosslink without being incorporated, e.g. carboxyl group activating hardener.
• the latter are preferably used.
• R 51 are -CH 2 -, -CH 2 -O-CH 2 -, -CH 2 -CONH-CH 2 -, -CH 2 -NHCONH-CH 2 -.
• suitable instant hardeners are those in Japanese laid-open patent applications 38 540/75, 93 470/77, 43 353/81 and 113 929/83 as well as in the U.S. Patent 3,321,313 compounds described.
• alkyl is in particular C 1 -C 20 alkyl optionally substituted by halogen, hydroxy, sulfo, C 1 -C 20 alkoxy.
• aryl is in particular optionally halogen.
• Sulfo, C 1 -C 20 alkoxy or C 1 -C 20 alkyl substituted C 6 -C 14 aryl, aralkyl, unless otherwise defined, is especially halogen.
• C 1 -C 20 alkoxy, sulfo or C 1 -C 20 alkyl substituted C 7 -C 20 aralkyl, alkoxy, unless otherwise defined, is in particular C 1 -C 20 alkoxy.
• X ⁇ is preferably a halide ion such as Cl ⁇ , Br ⁇ or BF 4 ⁇ , NO 3 ⁇ , (SO 4 2 ⁇ ) 1/2 , ClO 4 ⁇ , CH 3 OSO 3 , PF 6 ⁇ , CF 3 SO 3 ⁇ .
• Alkenyl is in particular C 2 -C 20 alkenyl
• alkylene is in particular C 2 -C 20 alkylene
• Arylene especially phenylene, aralkylene, especially benzylene and alkaralkylene, especially xylylene.
• Suitable N-containing ring systems which can stand for Z, are on pages 8 and 9 shown.
• the pyridine ring is preferred.
• R 36 and R 37 together with the nitrogen atom to which they are attached form in particular a pyrrolidine or piperidine ring substituted by 2 oxo groups bonded in the o- and o'-position, the benzo, cyclohexeno or [2.2.1] - can be bicyclohexenocondensed.
• Acyl is especially C 1 -C 10 alkylcarbonyl or benzoyl; Carbalkoxy is especially C 1 -C 10 alkoxycarbonyl; Carbamoyl is in particular mono- or di-C 1 -C 4 -alkylaminocarbonyl; Carbaroxy is especially phenoxycarbonyl.
• Groups R 24 which can be split off by nucleophilic agents are, for example, halogen atoms, C 1 -C 15 alkylsulfonyloxy groups, C 7 -C 15 aralkylsulfonyloxy groups, C 6 -C 15 arylsulfonyloxy groups and 1-pyridinyl radicals.
• hardener In particular 50 to 500 g / m 2 , preferably 200 to 400 mg / m 2 , of hardener are used.
• the casting solution for the hardening layer has in particular a viscosity of 1 to 30 mPa.s, the hardening layer in particular a wet layer thickness of 3 to 30 ⁇ m.
• Polymers can be added to the layers containing binder.
• examples are Polyacrylamides, gelatin derivatives, polyacrylic acid or polymethacrylic acid or their salts, polyvinylpyrrolidone, polyvinyl alcohol or carboxyl groups Polyvinyl alcohol derivatives, polyvinylimidazole, polyethyl acrylate, polybutyl acrylate, Polyurethane latices, polyester dispersions.
• the silver halide photographic material can be a black and white material, e.g. an x-ray or graphic material, including a diffusion transfer reversal material (DTR). It is preferably a color photograph Material.
• DTR diffusion transfer reversal material
• color photographic materials are color negative films, color reversal films, Color positive films, color photographic paper, color reversal photographic Paper, color-sensitive materials for the color diffusion transfer process or the silver color bleaching process.
• Suitable supports for the production of color photographic materials are e.g. Films and films of semi-synthetic and synthetic polymers, such as Cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, Polyethylene terephthalate and polycarbonate and with a baryta layer or ⁇ -olefin polymer layer (e.g. polyethylene) laminated paper.
• These carriers can be colored with dyes and pigments, for example titanium dioxide. she 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 To improve the adhesion of the photographic emulsion layer, for example one 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 optionally intermediate layers and protective layers.
• Essential components of the photographic emulsion layers are binders, Silver halide grains and color couplers.
• gelatin is preferably used as the binder used.
• this can be wholly or partly by other synthetic, semi-synthetic or naturally occurring polymers can be replaced.
• Synthetic Gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, Polyacrylamides, polyacrylic acid and their derivatives, especially 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 by reaction with Alkylating or acylating agents or by grafting on polymerizable Monomers have been obtained are examples of this.
• the binders should have a sufficient amount of functional groups have so that sufficient by reaction with suitable curing agents resistant layers can be produced.
• Such 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 acidic or alkaline Be informed. 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 should be as possible contain low levels of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
• Silver halide can be used as halide, chloride, bromide or iodide or mixtures of which included.
• the halide content of at least one layer 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% consist of bromide.
• silver bromide iodide emulsions in the case of color negative and color reversal films, usually silver chloride bromide emulsions with a high chloride content up to pure silver chloride emulsions. It can are mostly compact crystals, e.g.
• the layers can also have tabular silver halide crystals in which 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 have, 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 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 exceed Deviate ⁇ 30% from the average grain size.
• the emulsions can besides the silver halide also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.
• the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) made from soluble silver salts and soluble halides become.
• the silver halide is preferably precipitated in the presence of the binder, e.g. the gelatin and can be in the acidic, neutral or alkaline pH range be carried out, preferably silver halide complexing agents can also be used.
• the latter include e.g. Ammonia, thioether, Imidazole, ammonium thiocyanate or excess halide.
• the merge the water-soluble silver salts and the halides are optional one after the other by the single-jet or simultaneously by the double-jet method or by any combination of both methods. Dosage is preferred with increasing inflow rates, the "critical" feed rate at which just no new germs are emerging, 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 kept constant or a defined pAg profile during precipitation is driven through.
• a certain pAg kept constant or a defined pAg profile during precipitation is driven through.
• inverse precipitation with excess of silver ions is also possible.
• the silver halide crystals can also be precipitated by physical precipitation Ripening (Ostwald ripening) in the presence of excess halide and / or Silver halide complexing agents grow.
• the growth of the emulsion grains can even be done predominantly by Ostwald ripening, whereby preferably a fine-grained, so-called Lippmann emulsion, with a less soluble emulsion mixed and redissolved on the latter.
• salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe be present.
• the precipitation can also be carried out in the presence of sensitizing dyes respectively.
• Complexing agents and / or dyes can be used with everyone render it 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. through pasta and washing, by flaking and washing, by ultrafiltration or by Ion exchanger.
• the silver halide emulsion generally undergoes chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, Silver halide and sensitizer concentration - until reaching the Sensitivity and fog optimum subjected.
• the procedure is e.g. with H. Frieser "The basics of photographic processes with silver halides” Pages 675-734, Akademische Verlagsgesellschaft (1968).
• the chemical sensitization with the addition of compounds of Sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (e.g. gold, platinum, palladium, iridium) continue to occur can thiocyanate compounds, surface-active compounds, such as thioethers, heterocyclic nitrogen compounds (e.g. imidazoles, azaindenes) or also spectral sensitizers (described e.g. by F. Hamer "The Cyanine Dyes and Related Compounds ", 1964, or Ullmann's Encyclopedia of Chemical Engineering, 4th edition, vol. 18, p. 431 ff. And Research Disclosure 17643 (Dec. 1978), chapter III) are added.
• thiocyanate compounds e.g. gold, platinum, palladium, iridium
• surface-active compounds such as thioethers
• heterocyclic nitrogen compounds e.g. imidazoles, azaindenes
• a reduction sensitization can with the addition of reducing agents (tin-II salts, amines, Hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid) by Hydrogen, due to low pAg (e.g. less than 5) and / or high pH (e.g. above 8) be performed.
• reducing agents titanium-II salts, amines, Hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid
• the photographic emulsions can be used to prevent the compounds Fog formation or to stabilize the photographic function during the Production, storage or photographic processing included.
• 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 such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can also 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 also 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 the silver halide emulsions before, during or after their maturation are added. Of course you can do the connections also other photographic layers associated with a halogen silver layer are to clog.
• the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can be surface-active Contains agents for various purposes, such as coating aids Prevention of electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (e.g. acceleration of development, high contrast, sensitization, etc.).
• agents for various purposes such as coating aids Prevention of electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (e.g. acceleration of development, high contrast, sensitization, etc.).
• mainly synthetic surface-active compounds (surfactants) Use: non-ionic surfactants, e.g. Alkylene oxide compounds, glycerol compounds or glycidol compounds, cationic surfactants, e.g.
• alkylamines quaternary ammonium salts, Pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants, containing one 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 an amino alcohol.
• Acid group e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants.
• Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters an amino alcohol.
• the photographic emulsions can be made using methine dyes or other dyes are spectrally sensitized.
• Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
• Sensitizers can be omitted if for a certain spectral range the intrinsic sensitivity of the silver halide is sufficient, for example the blue sensitivity of silver bromides.
• the differently sensitized emulsion layers do not become diffusing assigned monomeric or polymeric color couplers, which are located in the may be in the same layer or in an adjacent layer.
• the red-sensitive layers are usually cyan couplers, the green-sensitive layers of purple couplers and the blue-sensitive layers Assigned yellow coupler.
• Color couplers for generating the blue-green partial color image are usually Phenol or ⁇ -naphthol type couplers.
• Color couplers for generating the purple partial color image are usually Couplers of the 5-pyrazolone, indazolone or pyrazoloazole type.
• Color couplers for generating the yellow partial color image are usually couplers with an open chain ketomethylene grouping, in particular type couplers ⁇ -acylacetamide; suitable examples are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers.
• the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers act. The latter are derived from the 4 equivalent couplers from the fact that they contain a substituent in the coupling site, which at Clutch is split off.
• the 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that at the color coupling disappears or by the color of the image dye produced is replaced (mask couplers), and the white couplers, which react with color developer oxidation products result in essentially colorless products.
• Couplers are also to be expected, which in the Coupling point contain a cleavable residue, which during reaction with Color developer oxidation products are set free and either directly or after the primary split off one or more more Groups have been split off (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 Effectiveness unfolds, e.g. as a development inhibitor or accelerator.
• 2-equivalent couplers 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 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.
• Further Advantages for color rendering, i.e. Color separation and color purity, and for that Detail reproduction, i.e. Sharpness and graininess are too with such DIR couplers achieve, e.g. the development inhibitor not immediately as a result of Split off the coupling with an oxidized color developer, but only after one further follow-up reaction, which is achieved, for example, with a timing group.
• DIR couplers that release a development inhibitor that in the developer bath essentially ineffective photographically decomposed products are for example in DE-A-32 09 486 and in EP-A-0 167 168 and 0 219 713 described. With this measure, a trouble-free development and Processing consistency reached.
• DIR couplers especially those that have a well diffusible Development inhibitor can be split off by suitable Measures for optical sensitization, improvements in color rendering, e.g. achieve a more differentiated color rendering, such as in EP-A-0 115 304, 0 167 173, GB-A-2 165 058, DE-A-37 00 419 and US-A-4 707 436.
• the DIR couplers can be in a multi-layer photographic material various layers can be added, e.g. also insensitive to light or intermediate layers. However, they are preferably the photosensitive one Silver halide emulsion layers added, the characteristic Properties of the silver halide emulsion, e.g. their iodide content, the structure the silver halide grains or their grain size distribution influences the photographic properties achieved.
• the influence of the released Inhibitors can, for example, by incorporating an inhibitor scavenger layer be limited according to DE-A-24 31 223. For reasons of reactivity or Stability, it may be advantageous to use a DIR coupler that is in the respective layer in which it is introduced, one of that in this layer producing color deviating color forms when coupling.
• contrast and maximum density DAR or FAR couplers can be used, which are a development accelerator or split off an fogger.
• Such connections 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 US-A-4 618,572 and 4,656,123.
• BAR couplers (Bleach Accelerator Releasing Coupler) is referred to EP-A-193 389.
• DAR and FAR couplers mainly the effectiveness of the released in the clutch rest is desired and less on the color-forming properties of these couplers are also such DIR, Suitable DAR or FAR couplers, which are essentially colorless when coupling Products result (DE-A-15 47 640).
• the cleavable residue can also be a ballast residue, so that in the reaction with Color developer oxidation products coupling products are obtained that are diffusible are or at least weak or limited mobility have (US-A4 420 556).
• the material may also contain compounds other than couplers, which, for example, a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent Can release fogging or an anti-fogging agent, for example So-called DIR hydroquinones and other compounds, such as those described in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438 are described. Meet these connections the same function as the DIR, DAR or FAR couplers, except that they do not Form coupling products.
• a development inhibitor for example, a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent Can release fogging or an anti-fogging agent, for example So-called DIR hydroquinones and other compounds, such as those described in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640,
• 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 described.
• the high molecular color couplers are usually through Polymerization of ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
• Incorporation of the couplers or other compounds in silver halide emulsion layers can be done in such a way that first of the connection in question prepared a solution, a dispersion or an emulsion and then the Pouring solution for the layer in question is added. Choosing the right one Solvent or dispersant depends on the solubility of the compound from.
• Hydrophobic compounds can also be made using high-boiling Solvents, so-called oil formers, are introduced into the casting solution. Appropriate methods are described, for example, in US Pat. No. 2,322,027, US Pat. No. 2 801 170, US-A-2 801 171 and EP-A-0 043 037.
• polymeric oil formers are used instead of the high-boiling solvents.
• the compounds can also be in the form of loaded latices in the casting solution be introduced.
• anionic water-soluble compounds e.g. of dyes
• cationic polymers so-called Pickling polymers take place.
• Suitable oil formers are e.g. Alkyl phthalates, phosphonic 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 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, Tridecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate, Diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t-amylphenol, dioctylacelate, glycerol
• Each of the differently sensitized, light-sensitive layers can be made of consist of a single layer or two or more Silver halide emulsion partial layers include (DE-C-1121470). Are there red-sensitive silver halide emulsion layers often closer to the substrate arranged as green sensitive silver halide emulsion layers and these again closer than blue-sensitive, with generally between green-sensitive layers and blue-sensitive layers are not photosensitive yellow filter layer.
• the usually between layers of different spectral sensitivity arranged non-light-sensitive intermediate layers can contain agents which an undesirable diffusion of developer oxidation products from a photosensitive to another photosensitive layer with different prevent spectral sensitization.
• Suitable agents also called scavengers or EOP-catchers, are described in Research Disclosure 17,643 (Dec. 1978), Chapter 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.
• the Partial layer with higher sensitivity from the carrier can be arranged as the sublayer with less sensitivity.
• Sub-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. For example, all highly sensitive and all low sensitive layers in one Layer package can be summarized (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).
• the photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides and others.
• Examples are aryl-substituted Benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3 707 375), butadiene compounds (US-A-4 045 229) or benzoxazole compounds (US-A-3 700 455).
• Ultraviolet absorbing couplers (such as ⁇ -naphthol type cyan couplers) can also be used. and ultraviolet absorbing polymers can be used. This Ultraviolet absorbents can be fixed in a special layer by pickling be.
• 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 described.
• Certain layers of binder especially those furthest from the carrier removed layer, but also occasionally intermediate layers, especially if the most distant layer during manufacture can represent photographically inert particles of inorganic or organic Contain 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 Range from 0.2 to 10 ⁇ m.
• the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble in general alkaline developing bath can be removed from the photographic material.
• suitable polymers are polymethyl methacrylate, copolymers of Acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
• Additives to improve dye, coupler and white stability as well as Reduction of 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.
• 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 capability can be used as the color developer compound. to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes.
• 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- (4-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.
• the material is usually bleached immediately after color development and fixed.
• 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-hydroxyethylethylenediamine triacetic acid, Alkyliminodicarboxylic acids and of corresponding phosphonic acids.
• Suitable bleaching agents are also suitable Persulfates and peroxides, e.g. Hydrogen peroxide.
• the bleach-fixing bath or fixing bath is usually followed by washing, as countercurrent washing or from several tanks with their own water supply consists.
• Color reversal materials are first developed using a black and white developer, whose oxidation product does not react with Color couplers is capable. A diffuse second exposure then closes Development with a color developer, bleaching and fixing.
• 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 m 2 . The corresponding amounts of AgNO 3 are given for the silver halide application.
• polymer P-5 is used in the same amount in all layers.
• the wet scratch resistance was determined from samples of the processed material following method.
• the photographic recording materials are located with the layer side up on a horizontal sample holder in a with water from 10 ° DH and 38 ° C filled tub.
• the sample to be measured is completely water covered.
• the force (in N) with which the above steel ball the outermost protective layer of the sample presses so that it is on a Measuring distance of 20 cm length increases continuously from 0 to 10 N.
• the wet scratch resistance of the photographic material (in N) specified the force at which the first layer injury occurs after sample drying can be recognized on the measuring section by means of the human eye.
• Table 1 shows that photographic materials with a Are hardened immediately and contain the polymers according to the invention, have improved mechanical properties in the form of wet scratch resistance and the source factor. In addition, through Addition of CO-PVA does not affect the gloss of the materials.
• a color photographic recording material was produced as in Example 1 described.
• Layer 3 and layer 5 contain polymer P-3 in the same amount instead of polyvinyl alcohol.
• Layer 3 and layer 5 contain polymer P-4 in the same amount instead of polyvinyl alcohol
• Layer 3 and layer 5 contain polymer P-5 in the same amount instead of polyvinyl alcohol.
• Layer 3 and layer 5 contain the same amount of polymer P-7 instead of polyvinyl alcohol.
• the layer structures were processed according to Example 1.
• the processed samples were exposed to the light of a xenon lamp standardized for daylight and exposed to 4.2 x 10 6 lx.h. The percentage decrease in density was then measured at an initial density of 1.5.
• Example 2 the wet scratch resistance, swelling factor and gloss of the samples were determined. The results are summarized in Table 2. Layer structure Density decreases in% after 4.2 ⁇ 10 6 lx.h shine Wet scratch resistance in N Swelling factor 2.1 (comparison) 77 clear 4.7 3.3 2.2 (comparison) 20th frosted 4.2 3.8 2.3 (comparison) 22 clear 3.9 4.0 2.4 (according to the invention) 18th clear 5.4 3.0 2.5 (according to the invention) 20th clear 5.6 3.1 2.6 (according to the invention) 17th clear 5.6 2.9 2.7 (according to the invention) 19th clear 5.3 3.1 2.8 (comparison) 20th clear 3.8 4.2 2.9 (according to the invention) 19th clear 5.7 2.8 2.10 (according to the invention) 17th clear 5.5 2.7 2.11 (according to the invention) 18th clear 5.5 2.8
• Example 2 shows that in the combination of instant hardeners with the amino functional ones Polyvinyl alcohols both mechanically stable layers as well light stable materials can be obtained.
• a color photographic recording material was produced in accordance with Example 1.
• the layer structures were processed according to Example 1.
• a color photographic recording material was produced in accordance with Example 1.
• Example 1 The samples are processed as in Example 1.
• Table 4 shows that the addition of the invention Polymers the light stability of those already provided with dye stabilizers Dyes can be further improved.
• Gelatin layers were poured, the dry substance of which consisted of 15% by weight of a polymer of 66% by weight of polyvinyl alcohol and 34% by weight of vinyl alcohol modified with aminoacetaldehyde-dimethylacetal. The curing was carried out with different amounts of methylene bis-vinyl sulfone. Control examples contained pure gelatin. All layers were applied at 5.0 g dry matter / m 2 . The details are in Table 5.1. sample % By weight of gelatin % By weight of polymer Amount of hardener (meq / g dry substance) 5.1 100 0 0.10 5.2 100 0 0.15 5.3 100 0 0.30 5.4 85 15 0.10 5.5 85 15 0.15 5.6 85 15 0.30
• Samples 5.4-5.6 according to the invention are distinguished by all properties by the better values.

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• Spectroscopy & Molecular Physics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Plural Heterocyclic Compounds (AREA)
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• 1993
  • 1993-06-03 DE DE4318438A patent/DE4318438A1/de not_active Withdrawn
• 1994
  • 1994-05-23 US US08/247,875 patent/US5455154A/en not_active Expired - Fee Related
  • 1994-05-24 DE DE59408567T patent/DE59408567D1/de not_active Expired - Fee Related
  • 1994-05-24 EP EP94107919A patent/EP0627656B1/de not_active Expired - Lifetime
  • 1994-05-31 JP JP6139556A patent/JPH0713282A/ja active Pending

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