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
  • G03C2001/03535—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
  • G03C2001/03558—Iodide content

Definitions

• the invention relates to a photographic recording material having at least one silver halide emulsion layer with grains which have a layered grain structure.
• Silver halide crystals with a layered grain structure which therefore have a shell and at least one inner zone, are known.
• GB-PS 1 027 146 for example, crystals are described which have a core of silver bromide, a zone of silver bromide iodide above and a shell of silver bromide.
• Silver halide emulsions are known from DE-OS 3 205 896 and GB-A 2 095 853, the silver halide grains of which have a core of silver iodide and, above that, a shell of another silver halide.
• Silver halide grains which have a relatively iodide-rich zone on the inside and a relatively iodide-poor outer zone on top, are also known from European patent specification 0 006 543 and Canadian patent specification 1 155 325. According to example 4 of the European Patent document partially converts a silver chloride bromide emulsion with iodide. A fine-grained silver bromide emulsion is added to the resulting emulsion in the presence of silver halide solvents, and it can be assumed that the silver halide grains of the fine-grained silver bromide emulsion are deposited on the converted silver halides. From European patent 0 006 543 it is also known that the emulsions described therein react in a marked manner to the presence of DIR compounds during photographic processing.
• DIR couplers known from GB 953 454, which carry a substituent in the coupling site which is split off during the coupling with the liberation of a diffusing compound which inhibits the development of the silver halide.
• DIR connections are further described in US Pat. No. 3,227,554, DE-OS 2,853,362, US Pat. No. 4,315,040 and European patent application 70 183.
• DIR connections can be used to improve the color quality through interimage effects and improve image sharpness through edge effects, see e.g. C.R. Barr, J.R. Thirtle and P.W. Vittum, Phot. Sci. Engn., 13 (1969) 74).
• DIR compounds have also become known, from which inhibitors are split off during color development and which are deactivated after a certain time by a subsequent reaction in the color developer: this prevents accumulation of inhibitors in the developer bath.
• the object of the invention was to provide photographic recording materials with improved emulsions.
• a special task was to provide emulsions which enable a high edge effect in recording materials in the presence of DIR compounds.
• all zones of the crystals can also contain chloride.
• at least one zone in which the iodide content does not assume a maximum contains chloride, the chloride content within such zones preferably being at least 1.5 mol%, in particular at least 30 mol%.
• a zone in which the iodide content assumes a maximum is understood to be one whose iodide content is higher than that of the two immediately adjacent zones.
• the boundaries between the zones of different composition can be sharp or unsharp.
• the boundary between adjacent zones is defined in that the iodide content at the boundary is equal to the mean value of the iodide contents of the homogeneous regions of the adjacent zones.
• the following Table 1 contains a schematic overview of grains suitably constructed, but without the invention being restricted to these grain types.
• the zones are given in order from the grain surface to the center.
• the zone in the center is referred to as the "core".
• the silver halide grains to be used according to the invention can be produced using a variety of techniques (for example single entry, double entry, constant or accelerated material inflow, Ostwald solution).
• Photographically active compounds such as compounds of copper, thallium, lead, bismuth, cadmium, ruthenium, rhodium, palladium, osmium, iridium, platinum, gold, sulfur, selenium and tellurium can be present during the precipitation.
• the silver halide emulsions according to the invention can be monodisperse or polydisperse in terms of precipitation. They can be mixed with each other or with other types of emulsions.
• Monodisperse emulsions are particularly preferred in which 70% of the spheres of the same size as the emulsion grains have a diameter that is between 0.8 times and 1.3 times the most frequent ball diameter.
• the emulsions to be used according to the invention can be chemically sensitized by known methods, for example with active gelatin or with compounds of sulfur, selenium, tellurium, gold, palladium, platinum, iridium, the pAg values being between 5 and 10 and the pH values between 5 and 8 and temperatures can vary between 30 ° C and 90 ° C; thiocyanate derivatives, thioethers and heterocyclic nitrogen compounds such as imidazoles, azaindenes, azapyridazines and azapyrimidines can be added during chemical sensitization be.
• the emulsions according to the invention can be subjected to a reduction sensitization, for example by hydrogen, by low pAg (for example less than 5) and / or high pH (for example above 8), by reducing agents such as stannous chloride, thiourea dioxide and aminoboranes.
• the surface ripening nuclei can also be converted into so-called troglodyte nuclei (sub-surface nuclei) according to DE-OS 2 306 447 and US Pat. No. 3,966,476. Further methods are described in Research Disclosure No. 17643 of December 1978, Section III, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, P09 1 EF in the UK.
• 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). In this regard, reference is made in particular to Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 18, pages 431 ff and to the above-mentioned Research Disclosure No. 17643, section IV.
• the spectral sensitization can take place at any time during the preparation of the emulsion,
• 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 preferably contains DIR compounds. These can be present in a silver halide emulsion layer or in a layer assigned to it.
• the inhibitory substances released from the DIR compounds are preferably mercapto compounds, e.g. l-phenyl-5-nercaptotetrazole.
• the inhibitory substances are released immediately by reaction of the DIR compound with the developer oxidation product.
• the inhibitory substances are only released indirectly after they have been split off from a delay group.
• hydrocarbyl group is an aliphatic or aromatic hydrocarbon group, e.g. B. to understand an optionally substituted alkyl or aryl radical.
• Examples of aliphatic hydrocarbon radicals for which R 1 and R 2 can stand are alkyl groups with 1 to 18 carbon atoms, which can be straight-chain, branched or cyclic and optionally substituted by alkoxy, aroxy, aryl, halogen, carboxy or sulfo groups, such as Methyl, isopropyl, tert-butyl, dodecyl, heptadecyl, benzyl, phenylethyl, carboxy-tert-butyl and methoxypropyl.
• DIR compounds are also known from DE-OS 2,853,362 and US Pat. Nos. 3,227,554 and 4,315,070. Particularly preferred DIR compounds of this type are given in Table 2 below.
• a particularly striking increase in the edge effect occurs when DIR compounds are used if the silver halide emulsion assigned to the DIR compounds contains stabilizers, sensitizing dyes or other substances which can be adsorbed on the silver halide; Sulfur-containing heterocycles with an N atom in the ring system are particularly suitable for this purpose.
• 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 may contain a non-diffusing color coupler to produce the cyan partial color image, typically a phenol or QC naphthol type coupler.
• the green-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone type usually being 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 can be, for example, 6-, 4- and 2-equivalent couplers, including the so-called white couplers, which do not produce any dye when reacted with color developer oxidation products.
• Suitable couplers are at known for example from the publications “Farbkuppler” by W. Pelz in “Mitrtieen aus den Anlagenslaboratorien der Agfa, Leverkusen / Ober", 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 of December 1978, Section VII.
• 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 dispersed form in a manner known per se. 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.
• the dispersion of the respective compound thus obtained can then be mixed with the silver halide emulsion.
• so-called oil formers generally higher-boiling organic compounds, are also used 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 is usually arranged closer to the layer support than the green-sensitive silver halide emulsion layer unit and this in turn is closer than the blue-sensitive one.
• at least one of the units for recording green, red and blue light consists of at least two sub-layers.
• layer supports can be used for the materials according to the invention, for example supports made of cellulose esters, for example cellulose acetate and made of polyesters. Also suitable are paper supports, which can optionally be coated, for example with polyols finen, especially with polyethylene or polypropylene.
• supports made of cellulose esters for example cellulose acetate and made of polyesters.
• paper supports which can optionally be coated, for example with polyols finen, 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 Offenlegungsschrift 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing are suitable. 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 are known from German laid-open documents 2 439 551, 2 225 230, 2 317 672 and from Research Disclosure 17643, section XI indicated 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-phenylenedianine type, for example 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- ⁇ -hydroxyethylaniline sulfate; 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-M- ⁇ -hydroxyethyl-p-phenylenediamine. Further useful 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
• the material is usually bleached and fixed. Bleaching and fixing can be carried out 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.
• Emulsion A (comparison emulsion)
• a silver chloride bromide iodide emulsion was prepared by the process known from EP 0 006 543 and contained 5 mol% chloride, 92 mol% bromide and 3 mol% iodide. If one assigns a sphere with the volume of the crystal to each crystal, the most common value of the sphere diameter was 0.23 ⁇ m, 90% of the sphere diameter was larger than 0.17 ⁇ m and 90% of the sphere diameter was less than 0.45 ⁇ m.
• the habit of the crystals obtained was plate-like to isometric, the boundary surfaces were partly octahedral surfaces and partly curved surfaces.
• Emulsion B (homodisperse comparison emulsion)
• a silver bromide iodide emulsion containing 99.1 mol% bromide and 0.9 mol% iodide was prepared by the double-jet process.
• the emulsion was at 56 ° C. with 18 pmol Na 2 S 2 0 3 . 5H 2 O / mol Ag, 5.8 ⁇ mol HAuCl 4 / mol Ag and 340 pmol KSCN / mol Ag chemically ripened and then spectrally sensitized with 400 pmol of a sensitizer for the red spectral range per mol Ag.
• Emulsion C Emulsion C (invention)
• a three-zone silver bromide iodide emulsion containing 95.05 mole percent bromide and 4.95 mole percent iodide was prepared by the double run-in process.
• the emulsion was chemically ripened at 56 ° C. with 32 ⁇ mol Na 2 S 2 O 3 .5H 2 O / mol Ag, 10.2 ⁇ mol HAuCl4 / mol Ag and 610 ⁇ mol KSCN / mol Ag and then with 400 ⁇ mol im
• Example B used sensitizing dye per mole Ag spectrally sensitized.
• the emulsion was therefore made up of 3 zones (Table 4), zone 2 having more than 6% more iodide than the adjacent zones.
• Emulsion D (invention)
• the cube-shaped silver halide crystals had an edge length of 0.5 ⁇ m and were treated at 56 ° C with 24 ⁇ mol Na 2 S 2 O 3 .5H 2 O / mol A g , 7.3 pmol HAuCl 4 / mol Ag and 435 ⁇ mol KSCN / mol Ag chemically ripened for three hours and then spectrally sensitized with 400 ⁇ mol of the sensitizing dye specified in Example B per mol of Ag.
• Emulsion E (invention)
• the previously homogeneous grain is converted into a grain that consists of an inner zone with little iodide, an outer zone containing high iodide and a transition area (fuzzy zone boundary).
• the iodide content of the outer zone is essentially determined by the miscibility gap. After 20 minutes, the emulsion thus obtained is flocculated, washed and redispersed in 6 liters of water.
• This emulsion which contains a total of 12.5 mol% AgI and has an average grain diameter of 0.16 ⁇ , has the amount of a very fine-grained Ag (Br, Cl, I) emulsion (average grain diameter 0.1 p) with 0 , 4 mol% AgI and 2 mol% AgCl mixed, which contains an amount of silver corresponding to 500 g AgN0 3 and has a gelatin concentration of 27 g / kg.
• the emulsion mixture thus obtained is subjected to Ostwald ripening in the presence of 75 g of imidazole at 65 ° C., pH 7.0 and pAg 7.8.
• Emulsion G (invention)
• the emulsion is prepared as described in Example F. Only the composition of the halide mixture in one solution of the double inlet changes 477 g ammonium bromide and 97 g potassium iodide. The potassium iodide solution added after the double inlet contains 28 g of potassium iodide.
• the emulsion obtained after Ostwald ripening has an average grain diameter of approx. 0.5 ⁇ .
• the spectral sensitization was carried out as for emulsion F.
• the DIR compound was emulsified together with tricresyl phosphate and gelatin in a weight ratio of 1: 1.
• the casting solutions obtained in this way were poured onto a layer support (silver application: 3.0 g per m 2 ) and cured.
• the quantities given relate to 1 m 2 .
• the corresponding amounts of AgNO 3 are given for the silver halide application.
• the magnitude of the edge effects was determined on the four layer structures 2A, 2B, 2F and 2G exemplified here, as explained in Example 1.
• the measured values obtained with the macro density 1.0 (via fog) are entered in Table 7.
• the sharpness of the materials 2A, 2B, 2F and 2G was determined using the modulation transfer function (MTF).
• MTF modulation transfer function
• Table 8 shows the spatial frequencies (in lines per mm) at which the MTF has a value of 50%. From the higher MTF values in the emulsions according to the invention it can be seen that these deliver a higher image sharpness.
• the materials specified in this example are processed when the edge effect, the MTF and the interimage effect are determined using the same color negative method as in example 1.

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• 1984
  • 1984-02-11 DE DE19843404854 patent/DE3404854A1/de not_active Withdrawn
• 1985
  • 1985-01-30 DE DE8585100911T patent/DE3570774D1/de not_active Expired
  • 1985-01-30 EP EP85100911A patent/EP0152822B1/fr not_active Expired
  • 1985-01-31 US US06/696,901 patent/US4636461A/en not_active Expired - Lifetime
  • 1985-02-08 JP JP60022133A patent/JPS60258536A/ja active Granted

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