EP0627656A2 - Matériau d'enregistrement photographique - Google Patents

Matériau d'enregistrement photographique Download PDF

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Publication number
EP0627656A2
EP0627656A2 EP94107919A EP94107919A EP0627656A2 EP 0627656 A2 EP0627656 A2 EP 0627656A2 EP 94107919 A EP94107919 A EP 94107919A EP 94107919 A EP94107919 A EP 94107919A EP 0627656 A2 EP0627656 A2 EP 0627656A2
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EP
European Patent Office
Prior art keywords
alkyl
layer
silver halide
und
oder
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EP94107919A
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German (de)
English (en)
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EP0627656A3 (fr
EP0627656B1 (fr
Inventor
Günter Dr. Helling
Jean-Marie Dr. Dewanckele
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Agfa Gevaert AG
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Agfa Gevaert AG
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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 which is improved in terms of wet scratch resistance and storage stability.
  • Photographic materials essentially contain gelatin as a binder.
  • the binder-containing layers are crosslinked with a crosslinking or hardening agent in order to impart sufficient stability and strength to the materials in the dry and wet state and during processing.
  • Formaldehyde, formaldehyde hydrates or formaldehyde releasers were previously used as curing agents (US Pat. No. 2,739,059). After it was shown that aldehydes damage the color couplers contained in color materials, new hardeners were sought. Hardeners were then developed which do not have the disadvantages mentioned and which can be used in modern multiple pouring systems, such as cascade and curtain casters. These hardeners work very quickly and are referred to as quick and instant hardeners.
  • the present invention preferably relates to photographic materials which are hardened with these hardeners, in particular instant hardeners.
  • Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed immediately after casting, at the latest after 24 hours, preferably after 8 hours at the latest, to the extent 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).
  • the quick and instant hardeners have the disadvantage that due to their short hardening time the wet scratch resistance is too low and the swelling factor is too high.
  • gelatin as a binder is that the stability of the photographic material, in particular the light stability, is unsatisfactory.
  • a disadvantage of these compounds is that the hardening of these layers with instant hardening agents is adversely affected and the wet strength and swelling factor do not meet the requirements placed on modern photographic material.
  • the object of the present invention was therefore to provide a binder or binder additive for gelatin which enables hardening of the photographic layers with instant hardeners and avoids the disadvantages mentioned.
  • CO-PVA certain vinyl alcohol copolymers
  • 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.
  • 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 acetate and vinyl acetate (for example vinyl propyl acetate) , Acyl nitrile, methacrylonitrile, aromatic vinyl compounds (e.g.
  • styrene vinyl toluene, divinylbenzene, vinyl acetophenone, styrene sulfonic acid), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (e.g. vinyl ethyl ether), ester of maleic acid, N-vinyl-2-pyrrolidone, N-vinyl vinyl , 2-vinyl and 4-vinyl pyridine as well as acrylic acid and methacrylic acid.
  • vinyl alkyl ether e.g. vinyl ethyl ether
  • ester of maleic acid N-vinyl-2-pyrrolidone
  • N-vinyl vinyl 2-vinyl and 4-vinyl pyridine as well as acrylic acid and methacrylic acid.
  • Preferred comonomers are vinyl acetate, crotonic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, styrene sulfonic acid, acrylamido-2-methylpropanesulfonic acid, sulfoethyl methacrylate and vinyl sulfonic acid.
  • the compound of formula I contains either a copolymerized comonomer M with acidic groups and / or the group M 2.
  • I and j together represent 2 to 30 mol%.
  • the CO-PVA can have a statistical distribution of the comonomers or can be graft or block copolymers. In particular, they are copolymers with polyacrylic acid blocks.
  • polymers according to the invention are:
  • the CO-PVA according to the invention can be used as a binder in photographic materials without further binders.
  • mixtures with known binders such as gelatin, polyvinylpyrrolidone, polyvinyl alcohol are preferably used. Mixtures with gelatin are particularly preferred.
  • a weight ratio of CO-PVA: gelatin is generally set 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 binder-containing layers of photographic materials. It is also possible to use the copolymer according to the invention in only one or a few layers. For example, it is possible to crosslink this layer more strongly than the others by adding the CO-PVA in only one layer of the layer structure.
  • the layers can be hardened differently by adding different amounts of CO-PVA to different gelatin-containing layers. This makes it possible to set a hardening profile.
  • the CO-PVA are preferably used in at least two layers of the photographic material. In order to improve the light stability of dyes, a CO-PVA layer should be provided above and a CO-PVA layer below the layer containing the dye to be protected. It is irrelevant whether the layers containing CO-PVA are emulsion, substrate, intermediate or protective layers.
  • a CO-PVA-containing layer is preferably applied over and a CO-PVA-containing layer under the layer containing the pyrazoloazole coupler.
  • the stabilization of the purple dye obtained after processing can be improved by adding special dye stabilizers to the layer containing the purple coupler.
  • the dye stabilizers listed below are also suitable for stabilizing 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.
  • Alkyl, aryl, cycloalkyl and heterocyclyl radicals can be further substituted.
  • the following compounds are suitable examples of groups St-I to St-VIII:
  • 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 CO-PVA can be synthesized by the methods known from the literature (e.g. US 2,739,059).
  • a polymer with vinyl alcohol structural elements can be reacted with aminoalkyl aldehyde acetal.
  • the vinyl alcohol-vinylamine copolymers can be prepared by the method described in DE-33 26 187.
  • the CO-PVA and CO-PVA gelatin mixtures are hardened with quick and instant hardeners.
  • rapid and instant hardeners are understood to be those compounds which, in the test described below, bring about a layer melting point of at least 95 ° C. Immediate hardeners also meet the definition given at the beginning.
  • a coating solution containing gelatin and, based on the gelatin, 1% by weight of the hardening agent is poured onto a base, for example paper coated on both sides with polyethylene or cellulose triacetate film.
  • the coating is dried at pH 6.2 and 35 ° C and then immersed in a water bath which is continuously heated from 20 ° C to 100 ° C over at least 5 minutes.
  • the temperature, where the layer runs off the base, recognizable by the streaking, is referred to as the melting point.
  • the curing agents can be those which are incorporated into the binder, for example hydroxydichlorotriazine or divinyl sulfone hardeners, or those which bring about a crosslinking of the binders without being incorporated themselves, 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 -.
  • Alkyl unless defined otherwise, in particular optionally substituted by halogen, hydroxy, sulfo, C 1 -C 2 -alkoxy-substituted C 1 -C 2 -alkyl.
  • aryl is in particular C 6 -C 14 aryl, aralkyl, optionally substituted by halogen, sulfo, C 1 -C 20 alkoxy or C 1 -C 20 alkyl, unless otherwise defined, is in particular by 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 e , Br e or BF 4 ⁇ , NO 3 ⁇ , (SO 4 2 ⁇ ) 1/2 , ClO 4 ⁇ , CH 3 OSO 3 , PF 6 ⁇ , CF 3 SO 3 ⁇ .
  • Alkenyl is especially C 2 -C 2o alkenyl
  • alkylene is especially C 2 -C 2o alkylene
  • Arylene especially phenylene, aralkylene, especially benzylene and alkaralkylene, especially xylylene.
  • Suitable N-containing ring systems which can stand for Z, are shown on pages 8 and 9.
  • 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 used according to the invention can also 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 group-containing 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 (DTR) material. It is preferably a color photographic material.
  • DTR diffusion transfer reversal
  • 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 sheets of semisynthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or a-olefin polymer layer (e.g. polyethylene).
  • These carriers can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light.
  • the surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.
  • the color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.
  • Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.
  • gelatin is preferably used as the binder.
  • this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers.
  • Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers.
  • Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates.
  • Semi-synthetic gelatin substitutes are usually modified natural products.
  • Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose as well as gelatin derivatives, which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers, are examples of this.
  • the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
  • functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
  • the gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used. The production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff.
  • the gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
  • the silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide.
  • the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide.
  • silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions with a high chloride content are used up to pure silver chloride emulsions. It can be predominantly compact crystals, e.g.
  • platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
  • the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, 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, e.g. 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 e.g. Ammonia, thioether, imidazole, ammonium thiocyanate or excess halide.
  • the water-soluble silver salts and the halides are brought together either one after the other by the single-jet process or simultaneously by the doublejet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded.
  • the pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation.
  • so-called inverse precipitation with an excess of silver ions is also possible.
  • the silver halide crystals can also grow by physical ripening (Ostwald ripening), in the presence of excess halide and / or silver halide complexing agent.
  • the growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.
  • Salts or complexes of metals such as Cd, Zn, Pb, TI, Bi, Ir, Rh, Fe may also be present during the precipitation and / or physical ripening of the silver halide grains.
  • the precipitation can also be carried out in the presence of sensitizing dyes.
  • Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.
  • the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchanger.
  • the silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached.
  • the procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).
  • Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (eg gold, platinum, palladi um, iridium), thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic nitrogen compounds (eg imidazoles, azaindenes) or spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia) der Technische Chemie, 4th edition, vol. 18, p. 431 ff. and Research Disclosure 17643 (Dec. 1978), chapter 111) are added.
  • compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table eg gold, platinum, palladi um, iridium
  • thiocyanate compounds eg gold, platinum, palladi um, iridium
  • a reduction sensitization can be carried out with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid) using hydrogen, by means of low pAg (eg less than 5) and / or high pH (eg above 8) .
  • reducing agents titanium-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid
  • the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
  • Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are e.g. by 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. Heterocycles containing mercapto groups are particularly suitable, e.g.
  • Mercaptobenzthiazoles mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, these mercaptoazoles also being a water-solubilizing group, e.g. may contain a carboxyl group or sulfo group.
  • Other suitable compounds are published in Research Disclosure 17643 (Dec. 1978), Chapter VI.
  • the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
  • the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
  • the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • surface-active agents e.g. Saponin are mainly used as synthetic surface-active compounds (surfactants): non-ionic surfactants. e.g. Alkylene oxide compounds, glycerin compounds or glycidol compounds, cationic surfactants, e.g.
  • alkyl amines quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid or phosphoric ester group, ampholytic surfactants, e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.
  • an acid group e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid or phosphoric ester group
  • ampholytic surfactants e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.
  • the photographic emulsions can be spectrally sensitized using methine dyes or other dyes.
  • Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromides.
  • the differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it.
  • cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.
  • Color couplers for producing the blue-green partial color image are generally couplers of the phenol or a-naphthol type.
  • Color couplers for generating the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type.
  • Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the a-acylacetamide type; suitable examples are a-benzoylacetanilide couplers and a-pivaloylacetanilide couplers.
  • the color couplers can be 4-equivalent couplers, but they can also be 2-equivalent couplers.
  • the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point which is split off during the coupling.
  • the 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products.
  • the 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling point, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, e.g. as a development inhibitor or accelerator.
  • Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
  • DIR couplers the development inhibitors of the azole type, e.g. Release triazoles and benzotriazoles are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416.
  • Other advantages for color rendering, i.e. Color separation and color purity, and for detail reproduction, i.e. Sharpness and graininess can be achieved with such DIR couplers, e.g. do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further subsequent reaction, which is achieved, for example, with a timing group.
  • DIR couplers which release a development inhibitor which is decomposed into essentially photographically ineffective products in the developer bath are described, for example, in DE-A-32 09 486 and in EP-A-0 167 168 and 0 219 713. This measure ensures trouble-free development and processing consistency.
  • DIR couplers in particular those which release an easily diffusible development inhibitor
  • suitable measures can be taken to improve the color rendering, e.g. achieve a more differentiated color rendering, as described, for example, in EP-A-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 added to a wide variety of layers in a multilayer photographic material, e.g. also light-insensitive or intermediate layers. However, they are preferably added to the photosensitive silver halide emulsion layers, the characteristics of the silver halide emulsion, e.g. whose iodide content, the structure of the silver halide grains or their grain size distribution influence the photographic properties achieved.
  • the influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it can be advantageous to use a DIR coupler which forms a color in the coupling in the respective layer in which it is introduced, which color differs from the color to be produced in this layer.
  • DAR or. FAR couplers are used that split off a development accelerator or an fogging agent.
  • Compounds of this type are, for example, in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-0 089 834, 0 110 511, 0 118 087 , 0 147 765 and in U.S.-A-4,618,572 and 4,656,123.
  • DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-15 47 640).
  • the cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).
  • the material may further contain compounds other than couplers, which can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR-hydroquinones and other compounds, as described for example in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.
  • couplers can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR-hydroquinones and other compounds, as described for example in US-A-4 636 546, 4 345 024, 4 684 604 and in DE
  • High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211.
  • the high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
  • the couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question.
  • the selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
  • Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-0 043 037.
  • oligomers or polymers instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
  • the compounds can also be introduced into the casting solution in the form of loaded latices.
  • anionic water-soluble compounds e.g. dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
  • suitable oil formers are 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, 2-ethylphosphate, tridecoxyphosphate, tri-ethylphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphat
  • Each of the differently sensitized, light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
  • red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • the green or Red-sensitive layers can be selected without the yellow filter layer, other layer arrangements in which, for example, the carrier blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.
  • the non-light-sensitive intermediate layers which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
  • Suitable agents which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP A-0 069 070, 0 098 072, 0 124 877, 0 125 522.
  • sub-layers of the same spectral sensitization can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains.
  • the sublayer with higher sensitivity will be located further away from the support than the sublayer with lower sensitivity.
  • Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, e.g. separated by layers of other spectral sensitization.
  • all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).
  • the photographic material can also 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 (USA-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 a-naphthol type cyan couplers
  • ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
  • Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
  • Suitable whiteners are e.g. in Research Disclosure 17,643 (Dec. 1978), Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.
  • Certain layers of binder may contain photographically inert particles of an inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).
  • photographically inert particles of an inorganic or organic nature e.g. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).
  • the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
  • the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath.
  • suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
  • Additives to improve dye, coupler and whiteness stability and to reduce the color fog can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, 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 made by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing processed, 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.
  • Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73, 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.
  • bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used.
  • Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
  • Persulfates and peroxides e.g. Hydrogen peroxide.
  • the bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.
  • the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent.
  • this stabilizing bath also acts as a final bath.
  • 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 amounts given relate in each case to 1 m 2. The corresponding amounts of AgNO 3 are given for the silver halide application.
  • the wet scratch resistance of samples of the processed material was determined according to the following method.
  • the photographic recording materials are placed upside down on a horizontal sample holder in a tub filled with water at 10 DH and 38 ° C.
  • the sample to be measured is completely covered with water.
  • the force (in N) with which the above-mentioned steel ball presses on the outermost protective layer of the sample is set so that it continuously increases from 0 to 10 N over a measuring distance of 20 cm in length.
  • the force is given at which, after sample drying, the first layer damage on the measuring section can be recognized by the human eye.
  • the swelling factor of the samples is also measured as a measure of the crosslinking of the layer
  • Table 1 shows that photographic materials which have been hardened with an instant hardener and which contain the polymers according to the invention have improved mechanical properties which are expressed in the form of the wet scratch resistance and the swelling factor. In addition, the gloss of the materials is not affected by the addition of CO-PVA.
  • a color photographic recording material was prepared as described in Example 1.
  • 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 Ix.h. The percentage decrease in density was then measured at an initial density of 1.5.
  • Example 2 In addition, as in Example 1, the wet scratch resistance, swelling factor and gloss of the samples were determined. The results are summarized in Table 2.
  • Example 2 shows that the combination of instant hardening agents with the amino-functional polyvinyl alcohols gives both mechanically stable layers and light-stable materials.
  • 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 light stability of dyes already provided with dye stabilizers can be further improved by adding the polymers according to the invention.
  • 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.
  • Samples 5.4-5.6 according to the invention are distinguished by the better values for all properties.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • 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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP94107919A 1993-06-03 1994-05-24 Matériau d'enregistrement photographique Expired - Lifetime EP0627656B1 (fr)

Applications Claiming Priority (2)

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DE4318438A DE4318438A1 (de) 1993-06-03 1993-06-03 Fotografisches Aufzeichnungsmaterial
DE4318438 1993-06-03

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EP0627656A2 true EP0627656A2 (fr) 1994-12-07
EP0627656A3 EP0627656A3 (fr) 1995-03-22
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998013394A1 (fr) * 1996-09-27 1998-04-02 Sun Chemical Corporation Couches polymeres impermeables a l'oxygene et hydrosolubles
EP0927910A1 (fr) * 1997-12-31 1999-07-07 Eastman Kodak Company Composition de colloide hydrophile
EP0945754A1 (fr) * 1998-03-23 1999-09-29 Agfa-Gevaert N.V. Procédé pour la préparation des grains tabulaires (100) riches en bromure

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5691107A (en) * 1994-12-07 1997-11-25 Mitsubishi Paper Mills Limited Silver halide photographic photosensitive material
DE4445006C2 (de) * 1994-12-16 2000-05-25 Mitsubishi Paper Mills Ltd Lichtempfindliches photographisches Silberhalogenidmaterial
US6080536A (en) * 1998-03-23 2000-06-27 Agfa-Gevaert, N.V. Method of preparing (100) tabular grains rich in silver bromide

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Publication number Priority date Publication date Assignee Title
US2211323A (en) * 1938-07-27 1940-08-13 Eastman Kodak Co Vinyl acetal resin photographic coating
US3415653A (en) * 1964-12-21 1968-12-10 Eastman Kodak Co Silver halide photographic emulsions containing a copolymer of vinylamine and acrylic acid
US4350759A (en) * 1981-03-30 1982-09-21 Polaroid Corporation Allyl amine polymeric binders for photographic emulsions
US4315071A (en) * 1981-03-30 1982-02-09 Polaroid Corporation Polystyryl amine polymeric binders for photographic emulsions
JPS63153538A (ja) * 1986-08-21 1988-06-25 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
CA1330684C (fr) * 1988-04-15 1994-07-12 Robert Krantz Pinschmidt Jr. Methode pour la preparation de poly(alcool vinylique)-copoly(vinylamide) par un procede a deux etapes
DE3836945A1 (de) * 1988-10-29 1990-05-03 Agfa Gevaert Ag Fotografisches silberhalogenidmaterial und verfahren zu seiner verarbeitung
US5229260A (en) * 1991-03-13 1993-07-20 Konica Corporation Silver halide photographic light sensitive material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998013394A1 (fr) * 1996-09-27 1998-04-02 Sun Chemical Corporation Couches polymeres impermeables a l'oxygene et hydrosolubles
EP0927910A1 (fr) * 1997-12-31 1999-07-07 Eastman Kodak Company Composition de colloide hydrophile
EP0945754A1 (fr) * 1998-03-23 1999-09-29 Agfa-Gevaert N.V. Procédé pour la préparation des grains tabulaires (100) riches en bromure

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EP0627656A3 (fr) 1995-03-22
DE59408567D1 (de) 1999-09-09
US5455154A (en) 1995-10-03
EP0627656B1 (fr) 1999-08-04
DE4318438A1 (de) 1994-12-08

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