EP0580029A2 - Produit photographique de reproduction d'images en couleur - Google Patents

Produit photographique de reproduction d'images en couleur Download PDF

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Publication number
EP0580029A2
EP0580029A2 EP93110937A EP93110937A EP0580029A2 EP 0580029 A2 EP0580029 A2 EP 0580029A2 EP 93110937 A EP93110937 A EP 93110937A EP 93110937 A EP93110937 A EP 93110937A EP 0580029 A2 EP0580029 A2 EP 0580029A2
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EP
European Patent Office
Prior art keywords
low
blue
sensitive
sensitive layer
silver halide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP93110937A
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German (de)
English (en)
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EP0580029A3 (fr
Inventor
Detlef Dr. Brennecke
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication of EP0580029A2 publication Critical patent/EP0580029A2/fr
Publication of EP0580029A3 publication Critical patent/EP0580029A3/fr
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    • 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
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX 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
    • 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
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • G03C2007/3025—Silver 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
    • G03C2200/00—Details
    • G03C2200/19—Colour negative
    • 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
    • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
    • 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
    • Y10S430/164—Rapid access processing

Definitions

  • the invention relates to a color photographic recording material with camera sensitivity having at least two blue-sensitive silver halide emulsion layers which differ in their sensitivity, at least two green-sensitive layers which differ in their sensitivity and at least two red-sensitive layers which differ in their sensitivity, which is distinguished by improved sharpness distinguished.
  • Color photographic silver halide recording materials with camera sensitivity are usually built up with double or triple layers for each of the spectral ranges blue, green and red, silver bromide iodide emulsions usually being used as silver halide emulsions in order to achieve sufficient sensitivity.
  • the color-sensitive layers are divided into double or triple layers in order to obtain a good sensitivity-granularity ratio.
  • red- and green-sensitive layers must consist of high-chloride silver halide emulsions, since silver halide emulsions with a high bromide content of silver halide have an inherent sensitivity to blue light and must be separated from the light source by a yellow filter layer, which usually contains colloidal silver unless their blue sensitivity is to be exploited.
  • at least one blue-sensitive layer is built up from at least 80 mol% AgBr.
  • the material also contains a yellow filter layer, with the more sensitive silver halide emulsion layers for the green and / or red spectral range have high bromide fractions and are arranged under the yellow filter layer and under the low and / or medium-sensitive green and / or red-sensitized silver halide emulsion layers which contain high AgCl fractions.
  • the object of the present invention was to improve the sharpness of silver halide recording materials with camera sensitivity considerably without suffering any loss of sensitivity.
  • All of the low-sensitivity, and in the case of a three-layer structure, in particular all of the low- and medium-sensitive silver halide emulsion layers, are composed of silver halide emulsions with at least 50 mol% AgCl, preferably at least 80 mol% AgCl, but very particularly preferably the blue and green sensitive layers.
  • the equivalent spherical diameters of all silver halide emulsions are between 0.1 and 3 ⁇ m, in particular between 0.2 and 2 ⁇ m, with the equivalent spherical diameter 0.3 to 1 being particularly preferred for the low- and the low- and medium-sensitive blue-sensitive silver halide emulsions with a high chloride content Is 5 ⁇ m.
  • the highly sensitive partial layers for all spectral ranges can be silver bromide iodide emulsions in the usual way, which are separated from the light source if they are green or red sensitized by a conventional yellow filter layer, but it is also possible to use silver halide emulsions with a high chloride content in all layers differ essentially in their equivalent grain diameters.
  • the more sensitive silver halide emulsion layers are preferably arranged further away from the support than the less sensitive silver halide emulsion layers of the same spectral sensitization.
  • the remaining halide in the high chloride silver halide emulsions can be bromide and / or iodide.
  • the grain distribution of the emulsions can be monodisperse, ie the deviations from the mean grain diameter are not more than ⁇ 40%.
  • the emulsions can also be heterodisperse and have a broad grain distribution. Mixtures of several monodisperse emulsions with different grain diameters can also be used to produce the individual color layers, the grain diameter or the edge length of the different emulsions being up to 50 times, preferably up to 20, times, can differ It is also possible to mix heterodisperse emulsions with different mean grain diameters or heterodisperse and homodisperse, whereby the mean grain diameter can also differ by 50 times.
  • the emulsions can be precipitated according to the methods described in Research Disclosure 32 569, May 1991 on pages 325 to 331, freed from inorganic salts and purified.
  • the color photographic emulsions with a high proportion of AgCl can be spectrally sensitized using methine dyes or other dyes. Dyes from the group of cyanine dyes, merocyanine dyes and complex merocyanine dyes are particularly suitable.
  • Res. Discl. Contains an overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and combinations which have a super-sensitizing effect. Vol. 176 , 176 43 (1978), Res. Discl. Vol. 225 , 22534 (1983) and EP-A 0 261 244, EP-A 0 243 099, DE 35 39 930, EP-A 0 178 097, GB 2 176 304, DE 35 26 670 and US 4 552 834.
  • Spectral sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a specific spectral range, for example if AgI or AgIBr was used as the host crystal for the epitaxial precipitation of AgCl.
  • the spectral sensitizers can the silver halide emulsions with high content of AgCl before, during or after physical ripening (Ostwald ripening) during the precipitation of the silver halide.
  • the spectral sensitizers can also be added to the silver halide emulsions before or during or after chemical ripening.
  • the spectral sensitizers can also be added to the emulsions shortly before casting.
  • Luminescent substances can also be added to the silver halide emulsions with a high proportion of AgCl, such as water-soluble cyanines and / or water-soluble merocyanines, xanthene dyes, acridine dyes, oxazine dyes, thiazine dyes, riboflavins, triacetal methane dyes, aminonaphthol dyes, pyrene dyes, porcelain dyes (coumarin dyes) 270 082).
  • AgCl such as water-soluble cyanines and / or water-soluble merocyanines, xanthene dyes, acridine dyes, oxazine dyes, thiazine dyes, riboflavins, triacetal methane dyes, aminonaphthol dyes, pyrene dyes, porcelain dyes (coumarin dyes) 270 082).
  • 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 the light-sensitive silver halide layer.
  • these color couplers can split off development-inhibiting substances (DIR couplers, development-accelerating substances (DAR couplers), or bleaching of the developed silver accelerating substances (BAR couplers).
  • DIR couplers development-inhibiting substances
  • DAR couplers development-accelerating substances
  • BAR couplers bleaching of the developed silver accelerating substances
  • the color couplers used should have a high reactivity and a good color yield.
  • the Absorption properties due to the required print compatibility should be in the following ranges: ⁇ max for yellow couplers approx. 450 nm ⁇ 2 nm, for magenta couplers approx. 551 nm ⁇ 3 nm and for cyan couplers approx. 696 nm ⁇ 3 nm.
  • the color couplers should have a high storage stability at high temperatures and / or high humidity, the stability against harmful gases, in particular formalin, should be good and the color images obtained after coupling should also be stable against light and also against dark reactions.
  • the color couplers used should also have high processing stability, ie fluctuations in the temperature, the concentration of the developing substances and the pH should have no effect on the results obtained. Therefore, 2-equivalent couplers are preferred, which have a higher reaction kinetics and enable the saving of silver.
  • the use of high molecular weight couplers is also particularly preferred.
  • Yellow coupler EP-A- 0 327 348, EP-A- 0 304 810, EP-A- 0 205 583, US 4 791 050, US 4 770 983, DE 3 741 088, DE 3 803 664.
  • Purple coupler EP-A- 0 232 101, EP-A- 0 326 406, EP-A- 0 320 776, EP-A- 0 081 768, EP-A- 0 309 158, EP-A- 0 294 681, EP-A-0 294 785, DE 3 730 557, DE 3 732 512.
  • cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.
  • the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
  • the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site that is split off during the coupling.
  • the 2-equivalent couplers include those that are colorless and those that have an intense intrinsic color , which disappears during the color coupling or is replaced by the color of the image dye produced (mask coupler), and the white couplers which, when reacted with color developer oxidation products, essentially give colorless products.
  • the 2-equivalent couplers also include couplers which contain a removable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been split off from the primary removed residue (e.g. DE-n 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, for example as a development inhibitor or accelerator.
  • Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
  • white couplers are essentially pyrazolones corresponding to the purple couplers, which have a non-removable substituent in the 4-position.
  • mask couplers are pyrazolone magenta couplers and naphthol cyan couplers which are in the coupling position contain an arylazo group or a cleavable group having an arylazo group.
  • DIR couplers the development inhibitors of the azole type, e.g. Triazoles and benzotriazoles are released in DE-A-2 414 006, 2 610 546, 2 659 417, 2 754 281, 2 726 180, 3 626 219, 3 630 564, 3 636 824, 3 644 416 and 2 842 063 described.
  • 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-167 168 and 219 713. This measure ensures trouble-free development and processing consistency.
  • DIR couplers are used, especially those that release a well-diffusible development inhibitor, suitable measures can be taken in the optical sensitization achieve improvements in color rendering, for example a more differentiated color rendering, as described, for example, in EP-A-115 304, 167 173, GB-A-2 165 058, DE-A-3 700 419 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 the incorporation of an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it may be advantageous to use a DIR coupler in the particular layer in which it is introduced is a color different from the color to be generated in this layer when coupling.
  • DAR or FAR couplers can be used, which release a development accelerator or an fogger.
  • Compounds of this type are, for example, in DE-A-2 534 466, 3 209 110, 3 333 355, 3 410 616, 3 429 545, 3 441 823, in EP-A-89 834, 110 511, 118 087, 147 765 and described in US-A-4,618,572 and 4,656,123.
  • DAR or FAR couplers Since in the DIR, DAR or FAR couplers the effectiveness of the residue released during the coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or. Suitable FAR couplers, which result in the coupling essentially colorless products (DE-A-1 547 640).
  • the cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).
  • the material may further contain compounds other than couplers, which can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR hydroquinones and other compounds, as described for example in US-A-4 636 546, 4,345,024, 4,684,604 and in DE-A-3 145 640, 2 515 213, 2 447 079 and in EP-A-198 438 are described. 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.
  • Couplers that release a bleaching accelerator (BAR coupler) is also possible.
  • the couplers or other compounds can be incorporated into silver halide emulsion layers in such a way that a solution, a dispersion or an emulsion is first prepared from the compound in question and then added to the casting solution for the layer in question.
  • the selection of the suitable solvent or dispersing agent depends depends on the solubility of the compound.
  • Methods for introducing compounds which are essentially insoluble in water by grinding processes are, for example in DE-A-2 609 741 and DE-A-2 609 742.
  • 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 Pat. Nos. 2,322,027, 2,801,170, 2,801,171 and EP-A. A-0 043 037.
  • oligomers or polymers instead of high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
  • the compounds can also be introduced into the casting solution in the form of loaded latices.
  • anionic water-soluble compounds e.g. dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers are, for example, alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
  • oil formers are dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert.-amylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-doxy-5-butyl-2-butyl
  • Suitable agents which are also called scavengers or EOP scavengers, are described in Research Disclosure 17.643 / 1978, Chapter VII, 17.842 / 1979, pages 94-97 and 18.716 / 1979, page 650 and in EP-A-69 070, 98 072 , 124 877, 125 522 and in US-A-463 226.
  • R1 and R2 are longer-chain alkyl radicals and the compound of the formula
  • the photographic material may further contain UV light absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives for improving the stabilization of dyes, couplers and whites, and for reducing the color fog and others.
  • Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film.
  • Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US-A 3 533 794), 4-thiazolidone compounds (US-A 3 314 794 and 3 352 681), benzophenone compounds (JP-A 2784/71), cinnamic acid ester compounds (US-A 3 705 805 and 3 707) 375), butadiene compounds (US-A 4 045 229) or benzoxazole compounds (US-A 3 700 455).
  • Ultraviolet absorbing couplers such as ⁇ -naphthol type cyan couplers
  • 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 December 1978, page 22 ff, Unit 17,643, Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.
  • binder layers in particular the layer furthest away from the carrier, but also occasionally intermediate layers, especially if they represent the layer furthest away from the carrier during production, can contain photographically inert particles of an inorganic or organic nature, e.g. as matting agents or as spacers (DE -A 3 331 542, DE-A 3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter XVI).
  • photographically inert particles of an inorganic or organic nature e.g. as matting agents or as spacers
  • the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
  • the spacers are insoluble in water and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath.
  • suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
  • Suitable formalin scavengers are e.g. open chain or cyclic urea derivatives.
  • Additives to improve dye, coupler and whiteness stability and to reduce the color fog can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes, p- Alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
  • the emulsion layers or adjacent layers or the back layers of the photographic support material can also contain antistatic substances (Res. Discl. Vol. 176 (1978) No. 176 43 Chapt. XIII; EP-A. 0 243 099).
  • the high AgCl emulsions may also contain compounds that accelerate development. These compounds can be precursors of developing substances (US 3,342,597, 3,342,599; Res. Discl. Vol. 148 , No. 148 50 and Vol. 151 , No. 151 59). However, developer compounds such as 1-phenyl-3-pyrazolidone and other compounds can also be added to the emulsion layers or adjacent layers (JP-N 64339/81, 144547/82, 211147/82, 50532/83, 0536/83, 50533/83 , 50534/83, 50535/83, 115438/83).
  • the layers of the photographic recording material can be hardened with the usual hardening agents.
  • hardening agents which crosslink exclusively via the amino groups of the gelatin and those hardening agents which activate the carboxyl groups inherent in the gelatin, so that a second reaction with the amino group of the gelatin results in a Crosslinking takes place through the formation of isopeptide groups.
  • a third group of hardening agents crosslink the gelatin via the carboxyl group of the gelatin.
  • Hardening agents which crosslink via the amino groups of the gelatin are, for example, formaldehyde, glutaraldehyde and similar aldehyde compounds; Diacetyl, cyclopentadione and similar ketone compounds: bis (2-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds containing reactive halogen (US 3,288,775, US 2,732,303 , GB 974 723 and GB 1 167 207). Also suitable are divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine and other compounds which contain reactive olefin compounds (US Pat.
  • N-hydroxymethylphthalimide and other N-methylol compounds (US 2,732,316 and US 2,586,168), isocyanates (US 3 103 437), aziridine compounds (US 3,017,280 and US 2,983,611), acid derivatives (US 2,725,294 and US 2,725,295) and halogen carboxyaldehydes such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and dichlorodioxane can be used.
  • epoxy compounds (US 3 901 537) and isoxazole type compounds (US 3 321 313 and US 3 543 292).
  • polymeric, non-diffusing hardening agents can be added to the gelatin emulsion.
  • These polymeric compounds can contain all functional groups which react with the amino groups or the carboxyl groups of the gelatin.
  • the polymeric backbone must contain water-solubilizing groups such as -SO3Na-, -COO-Na or other groups (DE 34 33 893).
  • Hardening agents which activate the carboxyl group of the gelatin and lead to crosslinking via isopeptide groups are those of the carbodiimide type (US 3 100 704) or of the carbamoylpyridinium type (DE 24 08 814), compounds with a phosphorus halogen compound (JP-A 113929/83), N- Carbonyloximide compounds (JP-A 43 353/81), N-sulfoximido compounds (US 4 111 926) dihydroquinoline compounds (US 4 013 468), 2-sulfonyloxypyridinium salts (JP-A 110 762/81), formamidium salts (EP-A-0 162 308 ) and compounds with two or more N-acyloximino groups (US 4,052,373).
  • Compounds which crosslink the gelatin via the carboxyl groups are preferably inorganic salts, such as chromium salts, zirconium salts and aluminum salts.
  • Aromatic, primary amine is advantageously suitable P-phenylenediamine series compounds such as 3-methyl-4-amino-N-ethyl-N-hydroxyethyl-aniline, 3-methyl-4-amimo-N, N'-diethylaniline, 3-methyl-4-amino-N- ethyl-N'- ⁇ -methanesulfonamidoethylaniline, or their acid salts.
  • the processing temperatures can vary from 18 ° C-50 ° C, a preferred temperature range is 30 ° C-40 ° C.
  • the pH of the developer can be between 9.5 and 13.5. A pH between 10.0 and 10.5 is particularly preferred.
  • the developer contains chloride ions in a concentration of 1.4. 10 ⁇ 2 mol / l to 2.8.10 ⁇ 1 mol / l, particularly preferably in a concentration of 2.8.10 ⁇ 2 mol / l to 7.10 ⁇ 2 mol / l.
  • the developer can also contain bromide ions in an amount of 0.5.10 ⁇ 4 mol / l to 1.25.10 ⁇ 3 mol / l, with a range of 1.25.10 ⁇ 4 mol / l to 3.72.10 ⁇ 4 mol / l being particularly preferred. l is preferred.
  • the color developer contains buffer substances such as carbonates, borates and phosphates of alkali metals to adjust the pH.
  • the developer can also contain stabilizing substances such as hydroxylamines, triethanolamine and alkali metal or ammonium salts, sulfites and bisulfites. Diethylhydroxylamine is particularly preferred as the stabilizing agent.
  • the developer may also contain organic solvents such as benzyl alcohols, diethylene glycol, etc.
  • the developer can contain complex-forming substances, such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, the alkali metal salts of the compounds mentioned being used.
  • complex-forming substances such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, the alkali metal salts of the compounds mentioned being used.
  • Other compounds that can be used as complexing substances are organic phosphorus compounds (Res. Discl. Vol. 181 , No. 181 70 (1979)).
  • the developer solution can also contain accelerators for development, such as benzyl alcohol or compounds from the pyridinium series (US 2,648,604, US 3,171,247).
  • the developer solutions can further contain cationic dyes, such as phenofuranin and polythioether (US 2,533,990, US 2,531,832, US 2,950,970, US 2,577,127 and US 3,201,242).
  • Developers which are particularly suitable for the emulsions with a high AgCl content can be found in WO 8 704 534, EP-A 080 805, EP-A-231 861, EP-A-234 292, EP-A- 243 096, EP-A-255 402, EP-A-293 917, EP-A 312 984, DE 3 243 907, US 4 183 756, US 4 766 057, US 4 774 167.
  • the developers can also contain anti-fogging agents such as N-containing heterocyclic compounds, e.g. Benzotriazoles, 6-nitrobenzimidazoles, 5-nitro-isoindazoles, 5-methylbenzotriazoles, 5-nitrobenzotriazoles, 5-chlorobenzotriazoles, 2-thiazolylbenzimidazoles, 2-thiazolylmethylbenzimidazoles, hydroxyazaindolizines, etc. 1-heterocyclobenzyl-benzophenol-benzotyl-benzophenol, -hydro-phenyl-benzophenol, etc. , 2-mercaptobenzothiazole can be used.
  • Mercapto-substituted aromatic compounds such as thiosalicylic acid can also be used. Combinations of such stabilizers (antifoggants) with developer substances can be found in EP-A-080 896, EP-A-246 624 and EP-A-255 784.
  • Combinations of the developer solutions described with special layer components e.g. special color couplers, sensitizing dyes, curing agents, etc. are in DE 3 301 105, EP-A-082 649, EP-A. 231 832, EP-A-232 770, EP-A-243 100 and US 4 766 57.
  • the color photographic material with the emulsions with a high content of AgCl is subjected to a bleaching and fixing process after development, it being possible to carry out the two processes separately or simultaneously as a so-called bleach-fixing process.
  • Compounds of polyvalent metals e.g. Fe (III) Co (III), Cr (IV), Cu (II), etc. as well as organic compounds, e.g. Peracids, quinones, nitroso compounds, etc. Examples include: ferricyanides, bichromates and / or organic complex salts of Fe (III) or Co (III).
  • Complex salts of the polyvalent metals with aminopolycarboxylic acids are also possible, such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanol-tetraacetic acid, citric acid, tartaric acid.
  • the bleaching agents are generally in the form of alkali or ammonium salts.
  • alkali metal or ammonium salts of thiosulfate, thiocyanate and also thioether and thiourea are suitable as fixing agents.
  • the solution contains both a bleach and a fixative.
  • the bleach bath can also contain bleach accelerators.
  • Such connections are e.g. Thiourea derivatives, heterocyclic compounds, thioethers, quaternary amines and thiocarbamoyl compounds. These connections are e.g. in US 4,506,007, US 4,578,345, US 5,605,611, DE 3,635,391, EP-A-147 087, EP-A-173 540.
  • the material After bleaching and fixing, the material is washed or treated with a stabilizing solution.
  • a stabilizing bath in which case the film generally runs through several baths according to the countercurrent principle, compounds such as inorganic phosphoric acids, aminopolycarboxylic acids, Phosphonocarboxylic acids are added.
  • the stabilizing baths can contain borates, phosphates, carbonates, etc. as buffer substances for setting a specific pH.
  • the stabilizer bath can also contain formalin and growth inhibitors for fungi and bacteria, for example isothiazolones, 4-thiazolylbenzimidazoles, halogenated phenolbenzotriazoles, benzoic acid, sulfonamides, etc. Furthermore, wetting agents, whiteners and hardeners can be added to the stabilizing solution.
  • formalin and growth inhibitors for fungi and bacteria for example isothiazolones, 4-thiazolylbenzimidazoles, halogenated phenolbenzotriazoles, benzoic acid, sulfonamides, etc.
  • wetting agents, whiteners and hardeners can be added to the stabilizing solution.
  • Such baths which are suitable for processing the silver halide emulsions with a high AgCl content, are described in EP-A 071 402, EP-A 165 805, DE 3 412 684, DE 3 412 857 and DE 3 436 862.
  • Table 2 shows the material structures of different color negative materials, two comparison materials and two materials according to the invention.
  • the materials are adjusted to a photographic sensitivity of 24 DIN (200 ASA) and differ only, as shown in Table 2, by using different emulsions, which are characterized in Table 1: Blue, green, red layer means a comparatively highly sensitive layer, blue, green, red layer a comparatively low-sensitive layer.
  • Table 1 Emulsion [No.] Halide composition [Cl / Br / I] average grain size [ ⁇ m] Grain size distribution (rel.
  • Table 3 shows which emulsions are used in which layers of which materials.
  • Table 4 shows the measured transmission factors characterizing the sharpness of the specified materials when exposed to blue, green and red light at different spatial frequencies, in lines / mm.
  • the claimed materials have improved sharpness properties compared to the comparison materials.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP93110937A 1992-07-21 1993-07-08 Produit photographique de reproduction d'images en couleur. Withdrawn EP0580029A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4224026 1992-07-21
DE4224026A DE4224026A1 (de) 1992-07-21 1992-07-21 Farbfotografisches Aufzeichnungsmaterial

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EP0580029A2 true EP0580029A2 (fr) 1994-01-26
EP0580029A3 EP0580029A3 (fr) 1995-05-10

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EP (1) EP0580029A3 (fr)
JP (1) JPH06161058A (fr)
DE (1) DE4224026A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE60033073T2 (de) 1999-01-29 2007-08-30 Fujifilm Corp. Photographisches, lichtempfindliches Silberhalogenidmaterial und Bildherstellungsverfahren
JP4733663B2 (ja) * 2006-07-27 2011-07-27 富士フイルム株式会社 ハロゲン化銀写真感光材料及びこれを用いた画像形成方法
US9615463B2 (en) * 2006-09-22 2017-04-04 Oscar Khaselev Method for producing a high-aspect ratio conductive pattern on a substrate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0273404A2 (fr) * 1986-12-26 1988-07-06 Fuji Photo Film Co., Ltd. Matériau photographique sensible à la lumière et procédé de développement de celui-ci
EP0466417A1 (fr) * 1990-07-09 1992-01-15 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière emmagasiné en rouleau et l'unité photographique pour celui-ci
EP0468780A1 (fr) * 1990-07-26 1992-01-29 Konica Corporation Méthode de formation d'une image photographique colorée

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0820718B2 (ja) * 1988-10-03 1996-03-04 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
DE69027880T2 (de) * 1989-04-04 1997-03-20 Fuji Photo Film Co Ltd Farbfotografisches lichtempfindliches Silberhalogenidmaterial

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0273404A2 (fr) * 1986-12-26 1988-07-06 Fuji Photo Film Co., Ltd. Matériau photographique sensible à la lumière et procédé de développement de celui-ci
EP0466417A1 (fr) * 1990-07-09 1992-01-15 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière emmagasiné en rouleau et l'unité photographique pour celui-ci
EP0468780A1 (fr) * 1990-07-26 1992-01-29 Konica Corporation Méthode de formation d'une image photographique colorée

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JPH06161058A (ja) 1994-06-07
DE4224026A1 (de) 1994-01-27
EP0580029A3 (fr) 1995-05-10
US5360704A (en) 1994-11-01

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