EP0895121A1 - Elément photosensible contenant une émulsion à l'halogénure d'argent sensibilisée chimiquement avec un composé chalcogénure - Google Patents

Elément photosensible contenant une émulsion à l'halogénure d'argent sensibilisée chimiquement avec un composé chalcogénure Download PDF

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EP0895121A1
EP0895121A1 EP98202305A EP98202305A EP0895121A1 EP 0895121 A1 EP0895121 A1 EP 0895121A1 EP 98202305 A EP98202305 A EP 98202305A EP 98202305 A EP98202305 A EP 98202305A EP 0895121 A1 EP0895121 A1 EP 0895121A1
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Prior art keywords
substituted
silver halide
group
atom
chalcogenic
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EP98202305A
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German (de)
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EP0895121B1 (fr
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Johan Loccufier
René De Keyzer
Antonius Rutges
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Agfa Gevaert NV
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Agfa Gevaert NV
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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
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/097—Selenium
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/098—Tellurium
    • 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
    • G03C2200/33—Heterocyclic

Definitions

  • the present invention relates to a photosensitive image-forming element, more particularly to a high sensitive photographic silver halide emulsion with improved photographic properties.
  • This compound can be for instance a sulphur compound, a gold salt or a combination of both. It has been noticed in recent years that chemical sensitization with a chalcogenic compound other than sulphur is increasingly practicized in order to enhance photographic sensitivity. These compounds in turn often give rise to an increasing tendency of fog formation and often to stability problems. Looking at these problems which are for instance related to selenium sensitization various suggestions have already been formulated in the patent literature. Examples of selenium compounds which were suggested for use in order to get an increased sensitivity were substituted selenourea (as described e.g. in EP-A 0 280 031, EP-A 0 458 278), selenoethers (e.g.
  • At least one of A 1 R 1 to A 4 R 4 contains a nucleophilic group bonded to the urea nitrogen atom through a 2 or 3 member chain and where each of R 1 , R 2 , R 3 and R 4 independently represents an alkylene, cycloalkylene, carbocyclic arylene, heterocyclic arylene, alkarylene or aralkylene group; and each of A 1 , A 2 , A 3 and A 4 independently is hydrogen or represents a carbocyclic, sulfinic, sulfonic, hydroxamic, mercapto, sulfonamido or a primary or secondary amino nucleophilic group.
  • the chalcogenic atom in the urea compounds of the Burgmaier patent is activated by the nucleophilic group which is generally called a neighbouring group.
  • This type of reactions is summarized by the term 'neighbouring group participation', describing all the intramolecular reactions and all the reactions which involve non-electrostatic through-space interactions between groups within the same molecule.
  • Another example is in principle also described in EP-A 0 458 278.
  • US-P 4,810,626 and EP-A 0 458 278 as well substantial increase of sensitivity can be realized with this type of chemical sensitizer but as in the other patent proposals described hereinbefore no clear demonstration is given that fog could be kept under control. Accordingly there still exists a strong demand for chemical chalcogenic sensitizers other than the corresponding S-sensitizers that can give high sensitivity in combination with an acceptable low fog level.
  • a photosensitive element which comprises on a support at least one photosensitive silver halide emulsion layer and at least one non-light sensitive layer, wherein the silver halide emulsion layer comprises a chalcogenic compound satisfying formula (1): wherein:
  • the invention also provides a method for chemically sensitizing a silver halide emulsion by means of a chalcogenic compound according to the formulae (1), (2) or (3) at least partly in the presence of a silver halide solvent and a spectral sensitizer at a pH-value situated between 3 and 10, a pAg-value situated between 6 and 11 and a temperature in the range of from 40 °C up to 95 °C.
  • Heterocyclic selenones are known for quite a long time in organic synthesis as usefull synthetic intermediates for functional group transformation such as the conversion of epoxides to double bonds (Calo et al, Synthesis, (1976) 200-201). Potentially they can be used for chemical sensitization of silver halide photographic emulsions in which treatment the photosensitivity is incrased. However, the reactivity of the basic products is too low to be useful under conventional circumstances, used for chemical sensitization, as illustrated by the use of 3-methyl-2-selenoxobenzothiazole (Ref-1) as chemical sensitizer.
  • Ref-1 3-methyl-2-selenoxobenzothiazole
  • the compounds used in the present invention can be prepared by conventional synthetic strategies. As an illustration, the synthesis of sensitizer I and VI will be described.
  • sensitizer I The synthesis of sensitizer I :
  • sensitizer VI The synthesis of sensitizer VI :
  • the amount of the chalcogenic compound of formulae (1), (2) or (3) which can be used in the material of the present invention can vary depending on the type of compound, the type of silver halide grain, the conditions of chemical sensitization, etc.
  • the amount of the said chalcogenic sensitizer is usually in the range of 10 -9 to 10 -3 but preferably in the range of 10 -8 to 10 -4 and more preferrably in the range of 10 -7 to 10 -5 mole per mole silver halide.
  • the introduction of the chemical chalcogenic sensitizer represented by formulae (1), (2) or (3) can be done in various ways before starting or during the chemical sensitization procedure.
  • Said chalcogenic sensitizers which are more or less water soluble can be added to the dispersion of silver halide crystals as an aqueous solution if desired mixed up with a water soluble organic solvent.
  • Said sensitizers which are not water soluble can be introduced after solving the compound in a water soluble organic solvent which is normally used for the introduction of water unsoluble products in a photographic silver halide emulsion.
  • An alternative way for the introduction of an unsoluble chemical chalcogenic sensitizer is using an 'oil-in-water' dispersion or if desired a dispersion as disclosed in EP-A 0 703 492 by T.Yoshida et al. In the last named patent the said compound is therefore added to the silver halide emulsion before chemical sensitization in the form of a solid partical dispersion soluble in water.
  • Combinations of the chalcogenic compounds of the present invention can be used but can also be combined with other chalcogenic or other more "classical" sensitizers.
  • the chemical sensitization itself can be carried out in the presence of a sulphur compound, a chalcogenic compound and if desired in the presence of a noble metal (e.g. gold).
  • a noble metal e.g. gold
  • the sensitization in the presence of the chalcogenic compound represented by formulae (1), (2) or (3) and if desired together with any other chemical sensitizer, can be used in combination with a reduction sensitization too.
  • a salt of a noble metal e.g., gold, iridium, palladium, platinum
  • gold salts are preferably used as noble metal sensitizer.
  • gold sensitizers which are often used include chloroauric acid, goldsulfide, chloroaurate salts, aurithiocyanate and goldselenide.
  • the amount of the noble metal sensitizer can vary between 10 -7 and 10 -2 mole per mole silver halide.
  • Sulfur sensitization can be carried out with sulphur compounds like thiosulphates, thioureas, rhodamines, etc.
  • the sulphur sensitizer can also be used in an amount of about 10 -7 to 10 -2 mole per mole silver halide.
  • a reducing compound like thiourea dioxide, hydrazine derivatives, sulphinic acid, polyamine compounds, stannous chloride, borane compounds, reductones like ascorbic acid, etc.
  • Reduction sensitization can also be carried out at a low pAg or at a high pH or at both and if desired at elevated temperature. This kind of sensitization is refered to 'silver ripening'. More information can be found in Research Disclosure, Vol307,307105 and in P.Glafkides "Chimie et Physique Photographic", P.Montel - Paris, 5 th Ed.,1987.
  • the chemical sensitization with compounds of the present invention satisfying formulae (1), (2) or (3) should be carried out in the presence of a silver solvent which preferably should be thiocyanate.
  • a silver solvent which preferably should be thiocyanate.
  • This should be added as a sodium, a potassium or an ammonium salt but it is not limited thereto.
  • the thiocyanate salt can be added before or during the addition of said compound of the invention and before, during or after the addition of any other chemical sensitizer which can be or should be used together with the said selenium sensitizer.
  • the amount of the thiocyanate which should be present together with said chemical sensitizer represented by formulae (1), (2) or (3) is limited between 10 -6 and 10 -1 mole per mole silver halide and preferably situated between 10 -5 and 10 -2 mole per mole silver halide.
  • the chemical sensitization has also to be carried out in the presence of a spectral sensitizer.
  • This can be a dye out of different classes including polymethine dyes comprising cyanines, merocyanines, tri-, tetra- and polynuclear cyanines and merocyanines, oxanols, hemioxanols, styryls, merostyryls and so on.
  • Many representitive examples of these dye-classes can be found in EP-A 0 618 492, EP-A 0 638 841, US-A 5,308,748, US-A 5,310,645 and US-A 5,338,656.
  • Some types of spectral sensitizers are preferably used for this invention. It concerns the symmetrical or the unsymmetrical cyanine dyes containing a benzoxazole, benzthiazole or benzimidazole nucleus.
  • spectral sensitizer sometimes used to get supersensitization, which means that in a certain region of the spectrum the sensitization is greater than that from any concentration of one of the dyes alone or that which would result from the additive effect of the dyes.
  • supersensitization can be attained by using selected combinations of spectral sensitizing dyes and other addenda such as stabilizers, development accelerators or inhibitors, brighteners, coating aids, and so on.
  • the chemical sensitization described in the present invention should be carried out within limited chemical and physical conditions. Therefore the pAg should be in the range of 6 till 11 but preferably between 7 and 10. Further the pH should be in the range of 3 to 10, preferably 4 to 8.5 while the temperature should be situated in the range between 40 to 95 degrees C, preferably between 45 to 85 degrees C, though there is no particular limitation to any of these conditions.
  • the silver halide emulsion can be prepared in various ways by conventional methods. These start always with a nucleation phase followed by a grain growth phase. In this last phase of the emulsion preparation reactants can be added to the reaction vessel in the form of solutions of silver and halide salts or in the form of preformed silverhalide nuclei or fine grains which easily dissolve in the precipitation medium.
  • the individual reactants can be added through surface or subsurface delivery tubes by hydrostatic pressure or by an automatic delivery system for maintaining the control of pH and/or pAg in the reaction vessel and of the rate of the reactant solutions introduced in it.
  • the reactant solutions or dispersions can be added at a constant rate or a constantly increasing, decreasing or fluctuating rate, if desired in combination with stepwise delivery procedures. More details about the possible ways in making a silver halide emulsion which can be principally used in practizising this invention are summarized in Res.Discl.,38957 (1996)591-639 section I-C.
  • additional chemical metal salts can be added for occlusion in the crystal lattice.
  • Such compound is replacing an appropiate of silver and halide ions in the silver halide lattice.
  • dopants can be distinguished from the metal complexes which are added just before coatingas an additive by EPR- or ENDOR-technique. These dopants can be used to modify the crystal structure or the crystal properties and can therefore be employed to influence many photographical properties like sensitivity, reciprocity failure, gradation, pressure sensitivity, fog, stability, etc.
  • Dopants which are introduced in emulsions of the present invention are those which can act as a permanent or as a non-permanent electron trap.
  • the doping procedure itself can normally be executed at any stage during the grain growth phase of the emulsion preparation. It is important to know that the dopants can also be added in an indirect way by the addition of a dispersion containing very fine soluble silver halide grains or nuclei comprising the dopant. More additional information about the introduction and the use of dopants in the emulsion crystals of this invention can be found in Research Disclosure, 38957 (sept. 1996), section I-D.
  • the photographic emulsions prepared in this way contain silver halide crystals comprising chloride, bromide or iodide alone or in combinations thereof.
  • Other silver salts which can be incorporated in a limited amount in the silver halide lattice are silver phosphate, silver thiocyanate, silver citrate and some other silver ⁇ salts.
  • the chloride and bromide halide can be combined in all ratios to form a silverchlorobromide salt.
  • Iodide ions however can be coprecipitated with chloride and/or bromide ions in forming a iodohalide with an iodide amount which depends on the saturation limit of iodide in the lattice with the given halide composition; this means up to a maximum amount of about 40 mole percent in silver iodobromide and up to at most 13 molevig in silver iodochloride both based on silver.
  • the composition of the halide can change in the crystal in a continous or discontinous way.
  • Emulsions containing crystals composed of various sections with different halide compositions are used for several photographic applications. So a structure with a difference in halide composition between the center and the rest of the crystal (what is called 'core-shell'-emulsion) or with more than two crystal parts differing in halide composition (called a 'band'-emulsion) may occur.
  • the changes in halide composition can be realised by direct precipitation or in an indirect way by conversion where fine silver halide grains of a certain halide composition are dissolved in the presence of the so-called host grains forming a 'shell' or 'band' on the given grain.
  • the crystals formed by the methods described above have a morphology which can be tabular or non-tabular.
  • the aspect ratio ratio of equivalent circular diameter to thickness
  • the major faces of the formed tabular grains can have a ⁇ 111 ⁇ or a ⁇ 100 ⁇ -habitus the structure of which is (respectively) stable or has to be stabilised (for instance by a 'habitus modifying agent').
  • the class of non-tabular grains there are a lot of possibilities which can be divided in the more regular shaped crystals or the crystals with a mixed crystal habit.
  • the photographic emulsions of the present invention can be comprised of silver chloride, silver bromide and silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof.
  • a hydrophilic colloid is used as a binder or a protective colloid for the emulsion or any other layer of the photographic material of the invention.
  • Gelatin is an advantageous hydrophilic colloid.
  • the preparation of conventional lime-treated or acid-treated gelatin has been descibed in e.g. "The Science and Technology of Gelatin", edited by A.G.Ward and A.Courts, Academic Press 1977, page 295 and further.
  • the gelatin can also be enzyme-treated as described in Bull.Soc.Sci.Phot.Japan, Nr 16, page 30 (1966)
  • Gelatin may, however, be replaced in part or integrally by synthetic, semi-synthetic, or natural polymers.
  • Synthetic substitutes for gelatin are e.g. polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyvinyl imidazole, polyvinyl pyrazole, polyacrylamide, polyacrylic acid, and derivatives thereof, in particular copolymers thereof.
  • Natural substitutes for gelatin are e.g. other proteins such as zein, albumin and casein, cellulose, saccharides, starch, and alginates.
  • the semi-synthetic substitutes for gelatin are modified natural products e.g.
  • gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents, by grafting of polymerisable monomers on gelatin or prehardened gelatins with blocked functional groups as a consequence of this prehardening treatment, cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates and even potato starch.
  • Part of gelatin may further be replaced with a synthetic or natural high-molecular material.
  • An interesting substitute for gelatin may be silica as has been described in the published EP-A's 0 392 092, 0 517 961, 0 528 476 and 0 649 051 and 0 704 749.
  • EP-A 0 528 476 a method of preparing a silver halide light-sensitive photographic material incorporating layers of silver halide precipitated in colloidal silica serving as a protective colloid is given.
  • the silver halides are prepared in colloidal silica, leading to emulsion crystals that are stable at the end of the precipitation, without however having a predictable mean crystal diameter and crystal size distribution.
  • the silver halide emulsions of this invention which are prepared in one of the ways described hereinbefore contain crystals which have a spherical equivalent diameter (SED) of not more than 1.5 ⁇ m but preferable less than 1.0 ⁇ m.
  • SED spherical equivalent diameter
  • the spherical equivalent diameter (SED) of the crystal represents the diameter of the sphere which has the same volume as the average volume of the silver halide crystals of the said emulsion.
  • the emulsions can be surface-sensitive emulsions which form latent images primarily on the surface of the silver halide grains or they can be emulsions forming their latent-image primarily in the interior of the silver halide grain. Further the emulsions can be negative-working emulsions such as surface sensitive emulsions or unfogged internal latent image-forming emulsions. However direct-positive emulsions of the unfogged, latent image-forming type which are positive-working by development in the presence of a nucleating agent, and even pre-fogged direct-positive emulsions can be used in the present invention.
  • the photographic elements comprising the said silver halide emulsions can include various compounds which should play a certain role in the material itself or afterwards in the processing, finishing or warehousing the photographic material.
  • the antifoggant prevents occurance of a fog while a stabilizer has a function of stabilizing the photographic property.
  • the antifoggant and the stabilizer are used in preparation, storage or processing stage of the photographic material.
  • the antifoging agent and the stabilizers can be azoles, mercaptopyrimidines, mercaptotriazines, azaindenes, etc. (see Res.Discl., 38957(1996) section VII)
  • the hydrophilic colloidal layer (silver halide emulsion layer, backing layer, antihalo-layer, etc.) of the photographic material can contain an inorganic or an organic hardening agent (see Res.Discl.,38957(1996) section IIB), brighteners (see Res.Discl.,38957(1996) section VI), light absorbers and scattering materials (see Res.Discl.,38957(1996) section VIII), coating aids (see Res.Discl.,38957(1996) section IXA), antistatic agents (see Res.Discl.,38957(1996) section IXC), matting agents (see Res.Discl.,38957(1996) section IXD) and development modifiers (see Res.Discl. ,38957(1996) section XVIII).
  • an inorganic or an organic hardening agent see Res.Discl.,38957(1996) section IIB
  • brighteners see Res.Discl.,38957(1996) section VI
  • light absorbers and scattering materials see Res.
  • the photographic element may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, ultraviolet absorbers and spacing agents.
  • Suitable additives for improving the dimensional stability of the photographic element are e.g. dispersions of a water-soluble or hardly soluble synthetic polymer e.g.
  • Suitable UV-absorbers are e.g. aryl-substituted benzotriazole compounds as described in US-A 3,533,794, 4-thiazolidone compounds as described in US-A 3,314,794 and 3,352,681, benzophenone compounds as described in JP-A 56-2784, cinnamic ester compounds as described in US-A's 3,705,805 and 3,707,375, butadiene compounds as described in US-A 4,045,229, and benzoxazole compounds as described in US-A 3,700,455 and those described in Res.Discl.,38957 (sept. 1996) Section VI, wherein also suitable optical brighteners are mentioned.
  • Spacing agents may be present of which, in general, the average particle size is comprised between 0.2 and 10 ⁇ m. Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic element, whereas alkali-soluble spacing agents usually are removed therefrom in an alkaline processing bath. Suitable spacing agents can be made e.g. of polymethyl methacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropylmethyl cellulose hexahydrophthalate. Other suitable spacing agents have been described in US-A 4,614,708.
  • any thickening agent may be used in order to regulate the viscosity of the coating solution, provided that they do not particularly affect the photographic characteristics of the silver halide emulsion in the coated photographic material.
  • Preferred thickening agents include aqueous polymers such as polystyrene sulphonic acid, dextran, sulphuric acid esters, polysaccharides, polymers having a sulphonic acid group, a carboxylic acid group or a phosphoric acid group as well as colloidal silica.
  • Polymeric thickeners well-known from the literature resulting in thickening of the coating solution may even be used in combination with colloidal silica. Patents concerning thickening agents are e.g.
  • the layer binder In order to reach a high hardening degree the layer binder should of course dispose of an acceptably high number of functional groups, which by reaction with an appropriate hardening agent can provide a sufficiently resistant layer.
  • functional groups are especially the amino groups, but also carboxylic groups, hydroxy groups, and active methylene groups.
  • Hardeners may be added to the antistress layer, covering one or more light-sensitive silver halide emulsion layers rich in chloride before or during the coating procedure, or to one or more of the said emulsion layers.
  • the binders of the photographic element can be hardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol, chromium salts e.g. chromium acetate and chromium alum, aldehydes e.g. formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin, dioxan derivatives e.g.
  • appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol, chromium salts e.g. chromium acetate and
  • the photographic elements can be coated on a variety of supports which can be flexible or rigid.
  • the flexible materials include plastic films and papers while the rigid materials include glass, metals, etc.
  • the surface of the support is generally subjected to undercoating treatment (like corona discharge, irradiation with ultraviolet rays, etc) to enhance the adhesion with the silver halide emulsion layer (see Res.Discl.,38957(1996) section XV and the references cited therein).
  • the photographic elements can be exposed to actinic radiation, specially in the visible, near-ultraviolet and near-infrared region of the spectrum, to form a latent image (see Res.Discl., 38957(1996) section XVI). This latent-image can be processed in order to form a visible image (see Res.Discl.,38957 (1996) section XIX).
  • any optional light source releasing a radiation corresponding to the sensitivity wavelength of the photographic material can be employed.
  • the light sources generally used include natural light, incandescent lamp, halogen lamp, mercurey lamp, fluorescent lamp and all types of flash light sources.
  • Light sources that emit light in the ultraviolet to infrared region can be also used as recording light sources.
  • Photographic materials can for example also be exposed to gas lasers, semiconductor lasers, light emitting diodes or plasma light sources. In the same way the material can be exposed to a LCD light source or to a fluorescent surface given by a phosphor stimulated with electron rays.
  • hydroquinone is incorporated in the photographic material itself while the processing liquid is an mere alkaline solution.
  • Ascorbic acid should be interpreted in a broad sense and includes ascorbic acid isomers, derivatives, salts and analogous compounds (including some reductones and reductic acid derivatives).
  • the most preferred compounds are ascorbic acid, isoascorbic acid and their salts.
  • Useful combinations of developers containing an ascorbic acid developing agent which should be preferably used in the scope of the present invention is described for many applications (in graphics, radiography, etc) in Res.Discl., 37152 (march 1995)185-224.
  • the photographic emulsions according of the present invention can also be used in multi-layered multicolor materials. These materials comprise a support and two or more silver halide emulsion layers that have different spectral sensitivities.
  • the multi-layered color photographic material generally comprises at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support.
  • a non-light sensitive layer may be provided between two or more emulsion layers having the same color sensitivity. Otherwise, another emulsion layer having a different color sensitivity can be provided between two or more emulsion layers having the same color sensitivity.
  • a light-reflecting layer such as a layer of silver halide grains can be provided under a high sensitive layer, particularly under a high blue-sensitive layer in order to enhance the sensitivity.
  • the silver halide material can also contain different types of couplers which can be incorporated in color photographic materials.
  • the red-sensitive emulsion layer contains generally a cyan coupler
  • the green-sensitive layer generally contains a magenta coupler
  • the blue-sensitive emulsion layer generally contains a yellow coupler. All the information which can be important for the application of the present invention in these type of materials is extensively described in Res.Discl.,38957 (sept. 1996) section X. More information in relation with the various color applications which belong also to the scope of the present invention, can be found in US-P 05,532,120 too.
  • Processing to form a visible dye image for colour materials means contacting the element with a colour developing agent in order to reduce developable silver halide and to oxidize the colour developing agent which in turn normally reacts with a coupler to form a dye (see Res. Discl.,38957(1996)section XX).
  • the solutions (1) and (2) were introduced into a reaction vessel during 35 seconds at 26 ml per minute using the double jet technique.
  • Said reaction vessel initially contained 2127 ml of distilled water at 51°C, 12.5 grams of potassium bromide and 6 grams of gelatin. After one minute the reaction temperature of this mixture was raised to 70°C in 20 minutes and a solution of 47.5 grams of phtalated gelatin in 475 ml of distilled water were added. After 6 minutes the neutralisation step was started.
  • Solution (1) was added to the reaction vessel at a rate of 7.5 ml per minute to reach a pAg value of 8.99 (-10 mV versus a saturated Ag/AgCl reference electrode), whereafter the first growth step was started.
  • a double jet precipitation was started using solutions (1) and (2) which continued for 45 minutes 44 seconds.
  • the flow rate of solution (1) was 7.5 ml per minute at the start, linearly increasing to 14.5 ml per minute at the end of the precipitation.
  • the pAg value was kept constant at 8.99. Thereafter the second neutralisation step was started.
  • Solution (1) was added to the reaction vessel at a rate of 7.5 ml per minute in order to reach a pAg value of 7.38, whereafter the precipitation further continued with a second growth step.
  • the emulsion was flocculated after addition of a small amount of polystyrene sulphonic acid and the acidification to a pH value of 3.4. After sedimentation the mother liquid was removed, distilled water added and remaining salts were washed out after repeating this procedure.
  • the AgBrI-emulsion prepared in this way contained crystals which have a mean spherical diameter of 0.964 mm and a thickness of 0,22 mm.
  • Triphenylselenofosfine (Ref-2) is used as reference selenium-compound:
  • the temperature is lowered till 38 °C while the pH is adjusted at 6.1 and the pAg at 8.87, immediately followed by the subsequent addition of an amount triazaindolizine sufficient to stabilize the emulsions and several wetting agents in order to coat the emulsions on a polyethylene terephthalate support.
  • Gelatine is added till the ratio of gelatine over silver nitrate is 1.0.
  • the resulting photographic material contained about 2.3 grams of AgNO 3 per m 2 as indicated in Table 1.2.
  • the hardening was realised by the addition of a bisvinylsulfonmethane compound.
  • the processing was carried out at 33 °C in a total processing-time of 90 sec by using G138 as developer and a diluted G334 (addition of 4 parts of demineralized water to 1 part G334) as fixer.
  • Both developer and fixer are commercial products which are trademarket names of Agfa-Gevaert.
  • the density which was realised after processing as a function of the light dose was measured and used to determine the following parameters:
  • This example demonstrates the possibilities of a silver halide emulsion comprising tabular AgBrI-crystals which have been chemically sensitized with a chalcogenic chemical sensitizer of the present invention compared with a chemical sensitizer which lack the neighbouring group participating action. It also illustrates the influence of other chemical sensitizers like sulphur and goldsalts.
  • reaction vessel 15.2ml of solutions 1 and 2 were introduced into a reaction vessel in 35 seconds using the double jet technique.
  • Said reaction vessel initially contained 2127 ml of distilled water at 51°C, 12.5 grams of potassium bromide and 6 grams of gelatin. After one minute the reaction temperature of this mixture was raised to 70°C in 20 minutes and a solution of 47.5 grams of phtalated gelatin in 475 ml of distilled water were added. After 6 minutes the neutralisation step was started.
  • Solution 1 was added to the reaction vessel at a rate of 7.5 ml per minute to reach a pAg value of 8.99 (-10 mV measured against a saturated Ag/AgCl reference electrode), whereafter the first growth step was started.
  • a double jet precipitation was started using solutions 1 and 2 which continued for 45 minutes 44 seconds. During this precipitation, the pAg value was kept constant at 8.99. The flow rate of solution 1 was 7.5 ml per minute at the start, linearly increasing to 14.5 ml per minute at the end of the precipitation. Thereafter the second neutralisation step was started.
  • Solution 1 was added to the reaction vessel at a rate of 7.5 ml per minute in order to reach a pAg value of 7.38, whereafter the precipitation further continued with a second growth step.
  • the emulsion was flocculated after addition of a small amount of polystyrene sulphonic acid and the acidification to a pH value of 3.4. After sedimentation the mother liquid was removed, distilled water added and remaining salts were washed out after repeating this procedure.
  • the AgBrI crystals of the emulsion prepaired in this way were containing 1 mol % of iodide and had a spherical equivalent diameter (SED) of 0.93 mm while the thickness was 0.22 mm.
  • SED spherical equivalent diameter
  • each emulsion was stabilized with 10 ml of 0.00375 mole/l 4-hydroxy-6-methyl-1,3,3a,7-tetra-azaindene and after addition of the normal coating additives the solutions were coated simultaneously together with a protective layer containing 0.7 g of gelatine per m2 per side on both sides of a polyethylene terephthalate film support having a thickness of 175 mm.
  • the resulting photographic material contained per side an amount of silver halide corresponding to 3.90 grams of AgNO3 per m2. Hardening of the layers was performed with a bisvinylsulfonmethane compound.
  • the preparation steps were a nucleation and a first neutralization step, followed by a first growth step, a second neutralization step and a second growth step.
  • reaction vessel 15.2 ml of solutions 1 and 2 were introduced into a reaction vessel in 35 seconds using the double jet technique.
  • Said reaction vessel initially contained 2.16 liter of distilled water at 51°C, 12.59 grams of potassium bromide and 6 grams of a low isoelectric point gelatin. After 25 seconds the reaction temperature of the mixture was raised to 70°C in 26 minutes including the addition of 47.5 grams of phthalated gelatin in 475 ml destilled water during the last 6 minutes.
  • solution 1 was added to the reaction vessel at a rate of 7.5 ml per minute to reach a pAg of 9.1, whereafter the first growth step was started.
  • a double jet precipitation was started using solutions 1 and 2 which continued for 46 minutes 44 seconds. During this precipitation, the pAg value was kept constant at 9.1.
  • the flowing rate of solution 1 was 7.5 ml per minute at the start, linearly increasing to 14.5 ml per minute at the end of the precipitation.
  • solution 2 was introduced at 7.8 ml per minute at the start linearly increasing till 15.0 ml per minute at the end keeping the pBr value at the same constant level. Further the second neutralisation phase was started.
  • Solutions 1 and 3 were injected during 61 minutes and 15 seconds in the reaction vessel at a rate of 7.5 ml per minute at the start linearly increasing to 22.5 ml per minute at the end of the precipitation.
  • the pAg was kept constant at 7.5.
  • the pH value was lowered to 3.5 with diluted sulphuric acid which was followed by the addition of 3.0 ml of a 14 % by weight solution of polystyrenesulphonic acid sodium salt and by a washing procedure using demineralized water of 11°C. Then another 116.5 grams of the same LIP-gelatine as used in the nucleation step was added to the solution which was further digerated at 45°C during 60 minutes.
  • the emulsion is therefore first adjusted at a pH value of 6.0 and a pAg value of 7.5 (measured at 40 °C) followed by the successive addition (measured per 500 grams of silver nitrate) of:
  • the sensitized emulsions were stabilized with 10.0 ml of a 3.75*10-3 molar solution of the following stabilizer: and cooled till 38 °C, followed by the addition of 3 ml of a concentrated fenol solution.
  • the coating was carried out on polyethylene terephthalate film support having a thickness of 175 mm, after the addition of a normal coating additive at a layer thichness where the amount of silver halide per square meter, expressed as the equivalent amount of AgNO3 (in g/m2), is 6.0.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP98202305A 1997-08-01 1998-07-08 Elément photosensible contenant une émulsion à l'halogénure d'argent sensibilisée chimiquement avec un composé chalcogénure Expired - Lifetime EP0895121B1 (fr)

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EP98202305A EP0895121B1 (fr) 1997-08-01 1998-07-08 Elément photosensible contenant une émulsion à l'halogénure d'argent sensibilisée chimiquement avec un composé chalcogénure

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EP97202395 1997-08-01
EP97202395 1997-08-01
EP98202305A EP0895121B1 (fr) 1997-08-01 1998-07-08 Elément photosensible contenant une émulsion à l'halogénure d'argent sensibilisée chimiquement avec un composé chalcogénure

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0458278A1 (fr) * 1990-05-21 1991-11-27 Fuji Photo Film Co., Ltd. Matériau photographique à halogénure d'argent
DE19635098A1 (de) * 1996-08-30 1998-03-05 Agfa Gevaert Ag Lichtempfindliche Silberhalogenidemulsion und fotografisches Material
DE19648008A1 (de) * 1996-11-20 1998-05-28 Agfa Gevaert Ag Farbfotografisches Silberhalogenidmaterial

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0458278A1 (fr) * 1990-05-21 1991-11-27 Fuji Photo Film Co., Ltd. Matériau photographique à halogénure d'argent
DE19635098A1 (de) * 1996-08-30 1998-03-05 Agfa Gevaert Ag Lichtempfindliche Silberhalogenidemulsion und fotografisches Material
DE19648008A1 (de) * 1996-11-20 1998-05-28 Agfa Gevaert Ag Farbfotografisches Silberhalogenidmaterial

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