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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
• • 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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03511—Bromide content
• • 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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03517—Chloride content
• • 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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03535—Core-shell grains
• • 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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/0357—Monodisperse emulsion

Definitions

• the invention relates to an emulsion rich in silver chloride, a photographic recording material and a method for producing photographic recordings.
• Silver halide emulsions which contain chloride, bromide, iodide or mixtures thereof as the halide.
• Silver bromide and silver bromide iodide emulsions are generally used for more sensitive recording materials.
• a disadvantage of the last-mentioned emulsions is that they have an intrinsic sensitivity in the blue spectral range. Therefore, in color recording materials, green and red sensitive layers are generally placed behind a filter that absorbs blue light. Furthermore, such emulsions cannot be developed as quickly as silver chloride emulsions.
• Chloride-containing silver halide emulsions are also known, the grains of which have a layered structure. Such grains have a core and at least one layer which surrounds the core and whose properties differ from the core (core / shell emulsions). It is known from DE-AS 1 169 290 and GB 1 027 146 to drop a silver chloride shell onto a silver bromide core.
• DE-OS 2 308 239 and US 3 935 014 relate to emulsions for producing directly positive images with silver halide grains which have a localized phase with a high silver chloride content.
• the zone Z Br rich in silver bromide can be present as a core or as a layer within the silver halide grain. Preferably 20% by volume of the silver halide of the grain is further from the crystal center than the zone Z Br rich in silver bromide.
• the silver halide grains in the bromide-rich zone Z Br and in areas other than halide can have chloride, bromide, iodide or mixtures thereof.
• the transition from the bromide-rich zone Z Br to an adjacent zone of a different composition can be sharp or continuous.
• the chloride content of the total halide content is at least 85, in particular at least 90 mol%.
• the zone Z Br rich in silver bromide consists essentially, for example at least 90%, or exclusively of silver bromide.
• the silver halide emulsions according to the invention can be prepared using the customary procedures (e.g. single entry, double entry, with constant or accelerated material flow). It is particularly preferred to use the double-inlet process under control of the pAg value.
• the precipitation of the silver halide can be carried out in the presence of conventional dopants, e.g. B. in the presence of Ir compounds.
• the silver halide grains can be designed, for example, as cubes, octahedra or tetradecahedra.
• the grain size is preferably between 0.1 and 2.5 ⁇ m, in particular between 0.2 and 1.0 ⁇ m.
• the emulsion has a narrow grain size distribution.
• at least 95% by weight of the grains have a diameter which does not deviate from the average grain diameter by more than 40%.
• the emulsions can also have a broad grain size distribution.
• at least 10%, preferably 20%, of the silver halide grains have a diameter which deviates from the average grain diameter by at least 40%.
• the present invention further relates to a photographic recording material which contains at least one silver halide emulsion layer according to the invention on a support.
• the invention further relates to a method for producing photographic recordings by developing an exposed recording material according to the invention.
• the emulsions according to the invention are preferably chemically sensitized to a high surface sensitivity on the grain surface. They can be chemically sensitized using known methods, e.g. with active gelatin or with compounds of sulfur, selenium, tellurium, gold, palladium, platinum, iridium, the pAg values between 4 and 10, the pH values between 3.5 and 9 and the temperatures between 30 ° C and 90 ° C can fluctuate;
• the chemical sensitization can be carried out in the presence of heterocyclic nitrogen compounds such as imidazoles, azaindenes, azapyridazines and azapyrimidines and thiocyanate derivatives, thioethers and other silver halide solvents.
• heterocyclic nitrogen compounds such as imidazoles, azaindenes, azapyridazines and azapyrimidines and thiocyanate derivatives, thioethers and other silver halide solvents.
• the emulsions according to the invention can be subjected to a reduction sensitization, e.g. by hydrogen, by low pAg (e.g. less than 5) and / or high pH (e.g. above 8), by reducing agents such as tin (II) chloride, thiourea dioxide and aminoborane.
• the surface ripening nuclei can also be present as troglodyte nuclei (sub-surface nuclei) according to DE-OS 2 306 447 and US Pat. No. 3,966,476. Other methods are described in the above. Research Disclosure No. 17643 in Section III.
• the emulsions can be optically sensitized in a manner known per se, e.g. with the usual polymethine dyes, such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
• polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
• Such sensitizers are from F.M. Hamer in "The Cyanine Dyes and related Compounds", (1964).
• EP-A 0 082 649 and in particular to Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 18, pages 431 ff and to Research Disclosure No. 17643, section IV given above.
• Spectral sensitization can affect anyone When the emulsion is made, ie during or after
• the commonly used antifoggants and stabilizers can be used.
• Suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are e.g. in the article by Birr, Z.Wiss.Phot. 47, 1952), pp. 2-58.
• Other suitable stabilizers and antifoggants are given in Research Disclosure No. 17643 above in Section IV.
• the recording material according to the invention is preferably a color photographic recording material.
• the color image is generated using color couplers. It is possible to let the color coupler diffuse into the recording material only during development.
• the photographic material itself contains the usual color couplers which can react with the oxidation product of developers, generally p-phenylenediamines, to form dyes.
• the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or oG-naphthol type.
• the green-sensitive layer can, for example, have at least one non- contain diffusing color couplers for producing the purple partial color image, color couplers of the 5-pyrazolone type being usually used.
• the blue-sensitive layer can contain, for example, a non-diffusing color coupler for generating the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
• the color couplers may be, for example, 6-, 4-, and act by 2-equivalent couplers, including the so-called Tokupp- he l, arising no dye on reaction with color developer oxidation products.
• Suitable couplers are known, for example, from the publications "Farbkuppler” by W. Pelz in "Mitanderen aus den Anlagens Laboratorien der Agfa, Leverkusen / llünchen", Volume III, page 111 (1961), K. Venkataraman in "The Chemistry of Synthetic Dyes", Vol. 4, 341 to 387, Academic Press (1971) and TH James, “The Theory of the Photographic Process", 4th Ed., Pp. 353-362, and from Research Disclosure No. 17643, Section VII.
• the recording material can also contain DIR compounds.
• DIR compounds are understood to mean those compounds which, when reacted with color developer oxidation products, release diffusing organic compounds which inhibit the development of silver halide.
• the inhibitors can be eliminated directly or via non-inhibiting intermediates.
• the color couplers and DIR compounds can be incorporated into the materials according to the invention by customary, known methods. If the compounds are soluble in water or alkali, they can be added in the form of aqueous solutions, optionally with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide. If the color couplers and DIR compounds are insoluble in water or alkali, they can be incorporated into the recording materials in a known manner in dispersed form. For example, a solution of these compounds in a low-boiling organic solvent can be mixed directly with the silver halide emulsion or initially with an aqueous gelatin solution and the organic solvent can then be removed.
• a solution of these compounds in a low-boiling organic solvent can be mixed directly with the silver halide emulsion or initially with an aqueous gelatin solution and the organic solvent can then be removed.
• oil formers generally higher-boiling organic compounds, which include the color couplers and DIR compounds to be dispersed in the form of oily droplets.
• the recording materials according to the invention preferably contain at least one silver halide emulsion layer unit for recording blue, green and red light.
• the red-sensitive silver halide emulsion layer unit can be arranged closer to the layer support than the green-sensitive silver halide emulsion layer unit and this in turn can be arranged closer than the blue-sensitive one. In the case of copying materials in particular, however, the position of the blue and red sensitive layers can also be interchanged.
• the recording material may optionally contain a yellow filter layer; However, this can be dispensed with in particular if at least the red- and green-sensitive layers contain an emulsion according to the invention.
• At least one of the units for recording green, red and blue light consists of at least two sub-layers. It is possible to combine sub-layers of different spectral sensitization according to their sensitivity.
• the usual substrates can be used for the materials according to the invention, e.g. Cellulose ester supports, e.g. Cellulose acetate and polyester. Also suitable are paper supports, which can optionally be coated, e.g. with polyolefins, especially with polyethylene or polypropylene.
• Cellulose ester supports e.g. Cellulose acetate and polyester.
• paper supports which can optionally be coated, e.g. with polyolefins, especially with polyethylene or polypropylene.
• polyolefins especially with polyethylene or polypropylene.
• hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, in particular gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others.
• Proteins in particular gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others.
• the layers can also contain other synthetic binders in dissolved or dispersed form, such as homopolymers or copolymers of acrylic or methacrylic acid or their derivatives, such as esters, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers.
• binders specified in Research Disclosure 17643 above in Section IX.
• the layers of the photographic material can be hardened in the usual manner, for example with hardeners of the epoxy type, the heterocyclic ethylene imine and the acryloyl type. Furthermore, it is also possible to harden the layers in accordance with the process of German laid-open specification 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers or the color photographic multilayer materials with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type. Further suitable hardening agents can be found in German Offenlegungsschriften 2,439,551, 2,225,230, 2 317 672 and from Research Disclosure 17643, Section XI above.
• the photographic materials according to the invention may also contain other substances, in particular plasticizers, wetting agents, screen dyes, light scattering agents, light reflecting agents, lubricants, antistatic agents, matting agents, etc.
• plasticizers in particular plasticizers, wetting agents, screen dyes, light scattering agents, light reflecting agents, lubricants, antistatic agents, matting agents, etc.
• Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, e.g. 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino-3-methyl-N-ethyl-N- ⁇ - (methanesulfonamido) ethylaniline sulfate hydrate; 4-amino-3-methyl-N-ethyl-N-B-hydroxyethylaniline sulfate; 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N-ß-hydroxyethyl-p-phenylenediamine.
• the p-phenylenediamine type e.g. 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino-3-methyl
• color developers are described, for example, in J.Amer.Chem.Soc. 73, 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, pages 545 ff.
• the color developers may contain the usual remaining ingredients, e.g. Lime and oxidation protection agents and agents for changing the fog, e.g. Bromide or stabilizers known per se.
• the material is usually bleached and fixed. Bleaching and fixation can NEN separately or together.
• the usual compounds can be used as bleaching agents, for example Fe 3+ salts and Fe 3+ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes etc.
• Iron-III complexes of aminopolycarboxylic acids in particular for example ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N, are particularly preferred -Hydroxyethylethylenediamintriessigkla, alkyliminodicarboxylic acids and corresponding phosphonic acids.
• Persulphates are also suitable as bleaching agents.
• a silver chloride emulsion is produced within 18 minutes by simultaneously pAg-controlled introduction of a 0.3 N NaCl and a 0.3 N AgNO 3 solution into a 2.4% gelatin solution brought to a temperature of 60 ° C.
• the average particle size is 0.16 ⁇ m and the emulsion has a monodisperse distribution.
• the crystals of this starting emulsion are enlarged to 13.4 times the volume by further addition of 2N NaCl and 2N AgNO 3 solutions.
• the pAg value is kept constant at 6.8.
• An AgBr shell is struck on the AgCl emulsion thus produced by double entry of 2 n KBr and 2 n AgNO 3 solutions.
• the precipitation is then continued by pAg-controlled double entry of 2n NaCl and 2n AgNO 3 solutions, an AgCl shell being applied to the previously precipitated AgBr layer.
• the emulsion produced in this way has an average particle diameter of 0.58 ⁇ m and a monodisperse distribution.
• the total content of AgBr is 6 mol%.
• a silver halide emulsion such as emulsion A is produced by pAg-controlled double enema, but it is used in all precipitation stages a mixture of NaCl / KBr was used as the alkali halide solution.
• This mixed halide solution contains 94 mol% NaCl and 6 mol% KBr; the solutions are used in the concentrations indicated for emulsion A.
• the silver halide emulsion produced in this way has an average particle diameter of 0.60 ⁇ m and has a monodisperse grain size distribution; the total AgBr content is 6 mol% and is homogeneously distributed throughout the crystal.
• Emulsions A and B are freed from the soluble salts by flocculation and washing in the usual way and then adjusted to a pAg of 7.6. Then both emulsions are chemically sensitized by adding sodium thiosulfate for 120 minutes at 55 ° C.
• the ripened emulsions are mixed with a sensi dye that absorbs in the green spectral range and a usual purple coupler emulsate and applied to a layer support. After exposure behind a step wedge and processing in the color development process known from British Journal of Photography, [1974] p. 597, the sensitometric data given in Table 1 are obtained.
• An emulsion C according to the invention is produced similarly to that described in Example 1. Like the emulsion A described there, the emulsion contains an AgBr layer, the AgBr content, based on the total halide, being 5 mol%. This emulsion C has a monodisperse particle size distribution and an average particle diameter of o.56 ⁇ m.
• an emulsion is produced by pAg-controlled double entry of aqueous silver nitrate and halide solutions, as described in EP-A 080 905 in Example 1 under Em-4. So that this comparison emulsion D can be compared sensitometrically with the emulsion C according to the invention, the AgCl core is enlarged before the AgBr shell is precipitated so that the final grain size of this emulsion is 0.57 ⁇ m.
• This emulsion also has a narrow (monodisperse) grain size distribution; the total AgBr content is 5 mol% and is only found in one layer on the crystal surface.
• Emulsions C and D are freed from the soluble salts by flocculation and washing in the usual way and then adjusted to a pAg value of 7.6. After the addition of sodium thiosulfate pentahydrate, both emulsions are chemically sensitized for 120 minutes at 55 ° C. Subsequently, the emulsions thus ripened are mixed with a dye which absorbs in the green spectral range and a conventional magenta coupler emulsate for sensitometric testing and applied to a layer support.
• the sensitometric values given in Table 2 are obtained.
• the sensitivity information is based on the comparison emulsion C.
• the emulsions C and D given in Example 2 are mixed after the chemical ripening with a sensitizing dye which absorbs in the blue spectral range and a yellow coupler emulsate and are poured onto a layer support.

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• 1984
  • 1984-03-15 DE DE19843409442 patent/DE3409442A1/de not_active Withdrawn
• 1985
  • 1985-03-05 EP EP85102440A patent/EP0154921B1/fr not_active Expired
  • 1985-03-05 DE DE8585102440T patent/DE3567745D1/de not_active Expired
  • 1985-03-06 US US06/708,720 patent/US4590155A/en not_active Expired - Fee Related
  • 1985-03-14 JP JP60049464A patent/JPS60222844A/ja active Pending

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