EP0949536A1 - Emulsion sensible à la lumière ayant des grains tabulaires (100) riche en chlorure et procédé pour préparer les mêmes - Google Patents

Emulsion sensible à la lumière ayant des grains tabulaires (100) riche en chlorure et procédé pour préparer les mêmes Download PDF

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Publication number
EP0949536A1
EP0949536A1 EP98201093A EP98201093A EP0949536A1 EP 0949536 A1 EP0949536 A1 EP 0949536A1 EP 98201093 A EP98201093 A EP 98201093A EP 98201093 A EP98201093 A EP 98201093A EP 0949536 A1 EP0949536 A1 EP 0949536A1
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EP
European Patent Office
Prior art keywords
grains
tabular
emulsion
silver
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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Application number
EP98201093A
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German (de)
English (en)
Inventor
Peter Verrept
Ann Verbeeck
Frank Louwet
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Agfa Gevaert NV
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Agfa Gevaert NV
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Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP98201093A priority Critical patent/EP0949536A1/fr
Priority to US09/256,239 priority patent/US6136524A/en
Priority to JP11097223A priority patent/JP2000056419A/ja
Publication of EP0949536A1 publication Critical patent/EP0949536A1/fr
Withdrawn legal-status Critical Current

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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
    • G03C1/0051—Tabular grain emulsions
    • G03C1/0053—Tabular grain emulsions with high content of silver chloride
    • 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
    • G03C1/46—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein having more than one photosensitive layer
    • 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
    • G03C2200/01—100 crystal face
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes

Definitions

  • the present invention is related with light-sensitive ⁇ 100 ⁇ emulsions having ⁇ 100 ⁇ tabular silver halide grains rich in silver chloride, a preparation method thereof and use of said emulsions in photographic materials.
  • High aspect ratio tabular grains exhibit several pronounced photographic advantages. Thanks to their particular morphology greater amounts of spectral sensitizers can be adsorbed per mole of silver halide if compared with classical globular grains. As a consequence such spectrally sensitized tabular grains show an improved speed-granularity relationship and a wide separation between their blue speed and minus blue speed. Sharpness of photographic images can be improved using tabular grains thanks to their lower light scattering properties, again if compared with conventional globular emulsion grains. In colour negative materials e.g. the conventional sequence of the light-sensitive layers can be altered and the yellow filter layer can be omitted. In developed black-and-white images high covering power is obtained even at high hardening levels.
  • An emulsion is generally understood to be a "tabular grain emulsion" when tabular grains account for at least 50 percent of the total grain projected area.
  • a grain is generally considered to be a tabular grain when the ratio of its equivalent circular diameter to its thickness is at least 1.5.
  • the equivalent circular diameter of a grain is the diameter of a circle having an area equal to the projected area of the grain.
  • Silver halide tabular grains rich in chloride can have parallel faces in the ⁇ 111 ⁇ crystal plane or in the ⁇ 100 ⁇ crystal plane, thus providing a tabular ⁇ 111 ⁇ or a tabular ⁇ 100 ⁇ habit respectively.
  • the desired ⁇ 100 ⁇ tabular grains of grains having a habit deviating from the desired one e.g. cubic grains or substantially cubic grains (having an aspect ratio of less than 1.5), needles (having a ratio of long edge length L to short edge length 1 of the cylinder of more than 10) and single twins (cubic ⁇ 100 ⁇ crystal having 1 single twin plane along ⁇ 111 ⁇ , ⁇ 311 ⁇ or ⁇ 411 ⁇ plane) is desired as well in favour of homogeneity of crystal habit.
  • the present invention thus further extends the teachings on tabular emulsions grains (or crystals) rich in silver chloride having a ⁇ 100 ⁇ crystal habit (having a ratio of long edge length L to short edge length 1 of the rectangle of not more than 10 and, more preferably not more than 5), more particularly teachings with respect to grains having an average aspect ratio of more than 5, an average equivalent grain or crystal diameter of at least 0.3 ⁇ m and a thickness of less than 0.25 ⁇ m.
  • a light-sensitive silver halide photographic emulsion comprising a colloidally stabilizing binder and ⁇ 100 ⁇ tabular silver halide grains containing at least 50 mole % of silver chloride, wherein at least, 70 % by number of all grains is provided by said tabular grains, exhibiting an average aspect ratio of at least 5 and an average equivalent circular grain diameter of at least 0.3 ⁇ m, wherein said tabular grains have an average thickness of less than 0.25 ⁇ m for at least 75 % by number of all tabular grains.
  • a method comprising performing at least three distinct precipitation steps in an aqueous medium in a reaction vessel, followed by desalting by means of washing after flocculation or by means of ultrafiltration, wherein said three distinct precipitation steps consist of a nucleation step followed by a first and a second growth step, said method being further characterized by introducing in the said reaction vessel, after the first growth step (and preferably before the second growth step), a block-copolymer according to the formula (I) as described hereinafter and in the claims.
  • the emulsion as claimed thus also comprises a block-copolymer according to the said formula (I) wherein said block-copolymer consists of hydrophilic polyoxyethylene units in an amount by number of at least three and hydrophobic polyoxypropylene block units in an amount by number of not more than one and ethylenediamine as tetravalent linking unit.
  • the flow rates can be monitored by e.g. magnetic valves.
  • the pAg is preferably maintained at a constant value, made optionally variable in order to provide growth without further nucleation.
  • the method wherein the three distinct precipitation steps are present is characterized by introducing in the said reaction vessel, after the first growth step (and more preferably before the second growth step) a block-copolymer according to the formula (I), wherein said block-copolymer contains, besides an ethylenediamine unit as tetravalent linking unit, at least three terminal hydrophilic polyoxyethylene groups and not more than one terminal hydrophobic polyoxypropylene block unit.
  • a representative block-copolymer according to the formula (I) is the commercially available copolymer TETRONIC 1508® of BASF, Ludwigshafen, Germany.
  • introducing the block-copolymer in the reaction vessel proceeds after the first growth step and before the second growth step.
  • the pH is preferably established at a value of between 2.0 and 10.0 and more preferably between 3.0 and 9.0.
  • the pH is preferably established at a value of between 2.0 and 10.0 and more preferably between 3.0 and 9.0.
  • This step can be performed by making use therefore of introducing in the reaction vessel at least one compound providing ions selected from the group consisting of iodide ions, bromide ions, complex anions as CN - , SCN - , SeCN - , etc.
  • M represents an element from group VIII in the periodic system of the elements (Table of Mendelejew), preferably being Ru 2+ , Os 2+ , Rh 3+ , Ir 3+ or Pt 2+ ;
  • Preferred group VIII metal ions used in order to introduce a crystal dislocation onto the nuclei formed are e.g. Ru 2+ , Os 2+ , Rh 3+ , Ir 3+ or Pt 2+ .
  • Especially preferred are complex ion compounds of ruthenium, and more preferably hexacyano-ruthenium salts.
  • Group VIII metal ions useful in the method of the present invention have e.g. been described in US-A's 4,981,781 (Ru,Fe,Rh,Os); 5,024,931 (Ru,Rh,Os,Ir, Pd,Pt); 5, 252,456 (Pt,Ir) and 5,360,712 and EP-A's 0 336 426 (Ru,Os); 0 336 427 (Ru,Os) ; 0 415 481 (Rh,Ir,Os,Ru,Fe,Co)and 0 762 192 (Ir) and in Research Disclosure No. 38957, Chapter I, D(3), published September 1, 1996. More recent simultaneous filings, dated January 30, 1998, are EP-Applications Nos. 98200280 and 98200281.
  • dopants in literature are ruthenium, rhodium and iridium. Combinations of one or more dopant(s) may be added, in the same or different preparation steps of the ⁇ 100 ⁇ tabular silver halide crystals rich in silver chloride.
  • iodide ions and/or bromide ions When use is made of iodide ions and/or bromide ions, these ions may be provided by means of an organic iodide or bromide releasing agent.
  • organic iodide or bromide releasing agent Such releasing agents have e.g. been described in US-A's 5,389,508; 5,482,826; 5,498,516; 5,524,660 and 5,527,664; and in EP-A 0 651 284.
  • Alternative techniques in order to create dislocations are however not excluded.
  • Crystal dislocation(s) in the nuclei performed by the method of the present invention are introduced in order to provide anisotropic growth of the said nuclei into ⁇ 100 ⁇ tabular grains.
  • Said physical ripening step following introducing said dislocation line or lines and growing the nuclei formed in the nucleation step during the first growth step immediately following said physical ripening step is preferably within a time interval from 2 to 30 minutes, more preferably from 2 to 10 minutes.
  • the first growth step is required in order to increase the "Ostwald ripening pressure" between "non-dislocated” and “dislocated” grains in order to stimulate Ostwald (physical) ripening during the physical ripening time between the first and the second growth step, in order to make disappear the "non-dislocated” grains.
  • a concentration of colloidally stabilizing binder in amount from about 0.05 %, more preferably from about 1 % and still more preferably from 5-10 % up to 100 % by weight of the total available amount of stabilizing binder in the dispersion medium in the reaction vessel before or during nucleation.
  • the binder used is a compound selected from the group consisting of gelatin, the block-copolymer corresponding to the formula (I) and colloidal silica or a combination thereof.
  • Gelatin is nearly always present, except when colloidal silica is e.g. present as a sole colloid besides the block-copolymer corresponding to the formula (I).
  • onium compounds more preferably phosphonium compounds, is highly preferred as has e.g. been disclosed in EP-A 0 677 773.
  • Use of colloidal silica in the preparation of ⁇ 100 ⁇ tabular grains has been described in EP-A 0 767 400.
  • gelatin having a methionine content of at most 4000 ppm is preferred and it is even more preferred to use gelatin having a calcium content of less than 40 ppm (so-called “calcium-free” gelatin).
  • Said "oxidized” gelatin thus has a methionine content of at most 4000 ppm, but in a more preferred embodiment said gelatin is oxidized to a degree in order to have a methionine content of at most 1500 ppm.
  • Gelatin being substantially free from calcium ions is also called “deionized” gelatin. Additional information about those specific kinds of gelatin have been dealt with in EP-Application No. 96203207, filed November 15, 1996.
  • a wash technique in order to remove the excess of soluble salts is applied.
  • Any conventional wash technique can be used e.g. washing with several water portions after flocculation by an inorganic salt or by a polymeric flocculating agent like polystyrene sulphonic acid.
  • Emulsion washing has e.g. been described in Research Disclosure N o 38957 (1996), Chapter III.
  • ultrafiltration is used as wash technique.
  • Such procedure has been disclosed e.g. in Research Disclosure, Vol. 102, Oct. 1972, Item 10208; in Research Disclosure Vol. 131, March, Item 13122 and in Mignot US-A 4, 334, 012.
  • the emulsion prepared according to the method of the present invention thus comprises ⁇ 100 ⁇ tabular silver halide grains containing at least 50 mole % of silver chloride, more preferably at least 70 mole % of silver chloride and still more preferably at least 90 mole % of silver chloride.
  • Additional gelatin, colloidal silica and/or block-copolymer according to the formula (I) may be added in a later stage of the emulsion preparation e.g. after washing, in order to establish optimal coating conditions and/or in order to establish the required thickness of the coated emulsion layer.
  • That gelatin can be conventional (calcium containing, thus not demineralized) non-oxidized gelatin, having high amounts of methionine, but calcium free and/or oxidized gelatin is not excluded.
  • a ratio by weight of gelatin to silver halide ranging from 0.2 to 1.0 is then obtained, wherein silver halide is expressed as an equivalent amount of silver nitrate.
  • At least 70 % by number, more preferably at least 75 % and still more preferably at least 90 % by number of all grains is provided by said tabular grains having an average equivalent circular grain diameter of at least 0.3 ⁇ m, e.g. from 0.3 ⁇ m up to 10 ⁇ m, preferably from 0.7 ⁇ m up to 5 ⁇ m and even more preferably from 0.7 up to 2.5 ⁇ m., wherein said tabular grains exhibit an average aspect ratio of at least 5, more preferably from 5 to 50 and still more preferably from 5 to 25; an average thickness of less than 0.25 ⁇ m for at least 75 % by number of all tabular grains present, preferably from 0.05 up to 0.20 ⁇ m.
  • the emulsion prepared according to the method of the present invention is an emulsion comprising ⁇ 100 ⁇ tabulair silver chloroiodide grains.
  • the iodide ions used therein are located at the surface of the ⁇ 100 ⁇ grains as a result of a iodide conversion step at the end of the preparation, thereby making the silver iodide concentration increase in the vicinity of the crystal surface and reaching the highest concentration at the crystal surface.
  • iodide ions are incorporated in the said silver chloroiodide grains by the method as described hereinbefore.
  • This is in one embodiment achieved by mixing a soluble chloride and a soluble iodide salt, like potassium iodide, in one or more of the halide solutions up to the desired mole % concentrations required in each preparation step or by a triple jet technique with separate addition of an iodide containing aqueous solution. Due to the about 10 6 times lower solubility of silver iodide ions in comparison with silver chloride, said iodide ions are able to displace chloride ions from the grain, a technique known in the art as conversion.
  • Iodide ions are in another embodiment incorporated into the silver halide crystal lattice by the addition of a previously prepared silver iodide micrate emulsion, also called Lippmann emulsion, composed of either pure silver iodide or mixed halides, but in a preferred embodiment iodide is provided by means of an iodide releasing agent.
  • Patent applications referring to methods wherein iodide releasing agents are used are e.g. EP-A's 0 563 701, 0 563 708, 0 561 415 and 0 651 284.
  • Even bromide releasing agents are not excluded in the precipitation steps according to the method of the present invention if bromide ions are incorporated in the ⁇ 100 ⁇ tabular grains rich in chloride prepared according to the method of the present invention.
  • Tabular silver halide emulsions comprising tabular ⁇ 100 ⁇ grains rich in silver chloride prepared by the method of the present invention can be chemically sensitized as described e.g. in "Chimie et Physique Photographique” by P. Glafkides, in “Photographic Emulsion Chemistry” by G.F. Duffin, in “Making and Coating Photographic Emulsion” by V.L. Zelikman et al, and in "Die Grundlagen der Photographischen Sawe mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968).
  • chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulfur e.g.
  • emulsions can be sensitized also by means of gold-sulfur ripeners, or gold-selenium ripeners, or gold-sulphur-selenium ripeners, wherein in addition of or instead of selenium ripeners tellurium compounds may be added, or by means of reductors e.g.
  • the silver halide emulsions under consideration can be spectrally sensitized with methine dyes such as those described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons.
  • Dyes that can be used for the purpose of spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • Oxacarbocyanines have been described e.g. in US-A 5,434,042.
  • Especially preferred green sensitizers in connection with the present invention are anhydro-5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyl-oxacarbocyanine hydroxide and anhydro-5,5'-dichloro-3,3'-bis(n.sulfopropyl)-9-ethyl-oxacarbocyanine hydroxide.
  • Imidacarbocyanines as e.g.
  • a suitable mixture of oxacarbocyanine and imidacarbocyanine spectral sensitizers that is applied in favour of decolouring properties and sensitometry is e.g. anhydro-5,5'-dichloro-3,3'-bis (n-sulfobutyl)-9-ethyl oxacarbocyanine hydroxide or anhydro-5,5'-dichloro-3,3'-bis(n-sulfopropyl)-9-ethyl-oxacarbocyanine hydroxide together with anhydro-5,5'-dicyano-1,1'-diethyl-3,3'-di(2-acetoxy-ethyl)ethyl-imidacarbocyanine bromide.
  • spectral sensitization In classical emulsion preparation spectral sensitization traditionally follows the completion of chemical sensitization. However, in connection with tabular grains, it is specifically considered that spectral sensitization can occur simultaneously with or even precede completely the chemical sensitization step.
  • the spectral sensitizers are preferably added even before digestion of an ultrafiltrated emulsion or redispersion of a flocculated and washed emulsion: chemical sensitization after spectral sensitization is believed to occur at one or more ordered discrete sites of the tabular grains.
  • chemical sensitization may e.g.
  • phenidone and derivatives proceed in the presence of one or more phenidone and derivatives, a dihydroxy benzene as hydroquinone, resorcinol, catechol and/or a derivative(s) therefrom as e.g. sulfodihydroxy aryl compounds described in EP-A 0 718 682, one or more stabilizer(s) or antifoggant(s), one or more spectral sensitizer(s) or combinations of said ingredients.
  • Especially 1-p-carboxyphenyl, 4,4' dimethyl-pyrazolidine-3-one may be added as a preferred auxiliary agent as disclosed in US-A 5,447,826.
  • gelatinous emulsion rich in silver chloride prepared according to the method of the present invention is further coated in hydrophilic layer(s) which may, just as non-light-sensitive layers of the photographic material according to this invention, comprise compounds preventing the formation of fog or stabilizing the photographic characteristics during production or storage of the photographic elements or during the photographic treatment thereof.
  • heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles (preferably 5-methyl-benzotriazole), nitrobenzotria-zoles, mercaptotriazoles, mercaptotetrazoles, in particular 1-phenyl-5-mercapto-tetrazole and acetamido-1-phenyl-5-mercaptotetrazole, mercaptopyrimidines, mercaptotriazines, mercaptoimidazoles, mercapto-thiadiazoles, mercapto-oxadiazoles, benzothiazoline-2-thione, oxazoline-thione, triazaindenes
  • gelatin may be added in a later stage of the emulsion preparation, e.g. after washing, in order to establish optimal coating conditions and/or in order to establish the required thickness of the coated emulsion layer.
  • a gelatin to silver halide ratio ranging from 0.2 to 1.0 is then obtained, wherein extra gelatin added is not required to have a composition as specific as in the preparation step of the grains according to the method of the present invention.
  • Another binder may also be added instead of or in addition to gelatin.
  • Useful vehicles, vehicle extenders, vehicle-like addenda and vehicle related addenda have been described e.g. in Research Disclosure N o 38957 (1996), Chapter II.
  • the gelatin binder of the photographic material having at least one gelatinous emulsion according to the present invention can be forehardened 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, bis-vinyl-sulfonylmethane or ethane and those substituted with hydroxyl groups in order to provide a better solubility in aqueous medium, chromium salts e.g. chromium acetate and chromium alum, aldehydes e.g.
  • N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin
  • dioxan derivatives e.g. 2,3-dihydroxy-dioxan
  • active vinyl compounds e.g. 1,3,5-triacryloylhexahydro-s-triazine
  • active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine
  • mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid.
  • the binder can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts as disclosed in US-A 4,063,952 and with the onium compounds disclosed in EP-A 0 408 143.
  • fast-reacting hardeners such as carbamoylpyridinium salts as disclosed in US-A 4,063,952 and with the onium compounds disclosed in EP-A 0 408 143.
  • the hydrophilic layer package of silver halide photographic materials comprising in one or more light-sensitive layers one or more ⁇ 100 ⁇ tabular silver halide emulsions rich in silver chloride crystals prepared according to the method of the present invention, has a swelling degree of not more than 200 %. Said swelling degree is determined by means of the following procedure: a sample of the coated material is incubated at 57 °C and 34% RH for 3 days, whereafter the thickness (a) of the layer assemblage is measured. Thereafter the sample is immersed in distilled water at 21°C for 3 minutes and the thickness (b) of the swollen layer is measured.
  • the swelling ratio is then calculated as: (b-a)/a x 100 (%) .
  • Another expression telling the same is that per gram of gelatin coated, not more than 2 g of distilled or demineralized water at 21°C is absorbed within 3 minutes.
  • gelatinous emulsions comprising ⁇ 100 ⁇ tabular grains rich in silver chloride of the present invention can be used in various types of photographic elements e.g. black-and-white silver halide photographic materials, like materials used for X-ray diagnostic purposes and microfilms, or colour sensitive materials.
  • Two or more types of tabular silver halide emulsions that have been prepared in the same way but which may have been prepared differently can be mixed for forming a photographic emulsion for use in photographic materials in accordance with the present invention.
  • the photographic material is a photographic material comprising a support and at least one light-sensitive silver halide emulsion layer on at least one side of said support, wherein said emulsion layer(s) comprise(s) one or more emulsion(s) containing ⁇ 100 ⁇ tabular silver halide emulsion grains prepared according to the method of the present invention.
  • said photographic material is a single or double side coated X-ray material.
  • the single-side coated X-ray material may contain one single emulsion layer, as it is the case for many applications, or it can be built up by two or even more emulsion layers.
  • a material with a single or a duplitized emulsion layer coated on one or both sides of the support thus contains at least one gelatinous silver halide emulsion according to the invention.
  • duplitized emulsions differing in photographic speed by at least 0.15 log E a gain in cross-over exposure in double side coated materials can be obtained.
  • the material contains blue, green and red sensitive layers each of which can be single coated as in most common colour positive materials, but may consist of double or even triple layers as in colour negative or colour intermediate applications.
  • said photographic material comprises at least two layers having negative image type silver halide emulsions adjacent to each other, wherein the emulsion layer more close to the support comprises at least one emulsion having tabular emulsion crystals selected from the group consisting of silver chloride, silver chlorobromide, silver chloroiodide and silver chlorobromoiodide having a ⁇ 100 ⁇ crystal habit, prepared according to the method as described hereinbefore, wherein the adjacent layer(s) farther from the support comprise(s) at least one emulsion having essentially cubic emulsion crystals selected from the group consisting of silver chloride, silver chlorobromide, silver chloriodide, silver chlorobromoiodide, silver bromide and silver bromoiodide.
  • This layer arrangement e.g. is particularly in favour of pressure insensitivity, but is also useful in order to improve image tone.
  • Other measures to improve image tone which may be used have e.g. been given in EP-A 0 789 266 wherein leuco-dyes are described, forming a dye by reaction with oxidized developer in the vicinity of the developed grains. Leuco-dyes have already earlier been described for this purpose in US-A 4,865,958.
  • the photographic material may contain several light-insensitive layers, e.g. a protective layer, one or more backing layers, one or more subbing layers, one or more intermediate layers e.g. filter layers and even an afterlayer containing e.g. the hardening agent(s), the antistatic agent(s), filter dyes for safety-light purposes, etc..
  • the photographic element of the present invention may further comprise various kinds of coating physical property modifying addenda as described in RD N o 38957 (1996), Chapter IX, wherein coating aids, plasticizers and lubricants, antistats and matting agents have been described.
  • Development acceleration can be accomplished by incorporating in the emulsion layer or adjacent layers various compounds, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US-A's 3,038,805; 4,038,075, 4,292,400 and 5,569,576 as well as in EP-A 0 634 688.
  • various compounds preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US-A's 3,038,805; 4,038,075, 4,292,400 and 5,569,576 as well as in EP-A 0 634 688.
  • the photographic element of the present invention may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-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. polymers of alkyl(meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters, acrylonitriles, olefins, and styrenes, or copolymers of the above with acrylic acids, methacrylic acids, ⁇ - ⁇ -unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulfoalkyl (meth)acrylates, and styrene sulphonic acids.
  • a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl(meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters,
  • 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 2784/71, 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 RD N o 38957 (1996), Chapter VI, wherein also suitable optical brighteners are mentioned. UV-absorbers are especially useful in colour materials where they prevent fading by light of the colour images formed after processing.
  • Spacing agents can 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.
  • the photographic material can contain several non-light sensitive layers, e.g. an antistress topcoat layer, one or more backing layers, and one or more intermediate layers eventually containing filter- or antihalation dyes that absorb scattering light and thus promote the image sharpness.
  • Suitable light-absorbing dyes used in these intermediate layers are described in e.g. US-A's 4,092,168, US-A 4,311,787, DE-A 2,453,217, and GB-Patent 7,907,440. Situated in such an intermediate layer between the emulsion layers and the support there will be only a small negligable loss in sensitivity but in rapid processing conditions decolouration of the filter dye layers may form a problem.
  • One or more backing layers can be provided at the non-light sensitive side of the support of materials coated with at least one emulsion layer at only one side of the support.
  • These layers which can serve as anti-curl layer can contain e.g. matting agents like silica particles, lubricants, antistatic agents, light absorbing dyes, opacifying agents, e.g. titanium oxide and the usual ingredients like hardeners and wetting agents.
  • the support of the photographic material may be opaque or transparent, e.g. a paper support or resin support.
  • a paper support preference is given to one coated at one or both sides with an ⁇ -olefin polymer, e.g. a polyethylene layer which optionally contains an antihalation dye or pigment.
  • an organic resin support e.g. cellulose nitrate film, cellulose acetate film, poly(vinyl acetal) film, polystyrene film, poly(ethylene terephthalate) or poly(ethylene naphthalate) film, polycarbonate film, polyvinylchloride film or poly- ⁇ -olefin films such as polyethylene or polypropylene film.
  • organic resin film is preferably comprised between 0.07 and 0.35 mm.
  • These organic resin supports are preferably coated with a subbing layer which can contain water insoluble particles such as silica or titanium dioxide.
  • a subbing layer which can contain water insoluble particles such as silica or titanium dioxide.
  • the photographic material containing ⁇ 100 ⁇ tabular grains prepared according to the method of the present invention can be image-wise exposed by any convenient radiation source in accordance with its specific application.
  • processing conditions and composition of processing solutions are dependent from the specific type of photographic material in which the ⁇ 100 ⁇ tabular grains rich in chloride prepared according to the present invention are applied.
  • materials for X-ray diagnostic purposes said materials may be adapted to rapid processing conditions in a developer containing hydroquinone as main developing agent or even free from hydroquinone: as a more ecological developing agent ascorbic acid, reductic acid or derivatives thereof may in part or integrally replace hydroquinone.
  • an automatically operating processing apparatus is used provided with a system for automatic replenishment of the processing solutions.
  • hydrophilic layers of which may have been forehardened e.g. by means of hardeners as set forth hereinbefore, may be processed using one-part package chemistry or three-part package chemistry, depending on the processing application determining the degree of hardening required in said processing cycle.
  • the first growth step was started: during the next 7 minutes and 14 seconds the silver nitrate solution was run into the reaction vessel at a constant rate of 10 ml per minute, together with the sodium chloride solution, which was added at a variable addition rate in order to maintain a constant UAg of +178 mV vs.a silver/silver chloride reference electrode.
  • the addition rate of silver nitrate was linearly increased from 10 to 15 ml/min. at the end of the first growth step, while maintaining UAg at a constant potential of +184 mV.
  • sodium nitrate solution was added during 29 min. and 45 seconds at a linearly increasing rate from 11 ml/min. up to 35 ml/min. while maintaining UAg at a constant potential of +159 mV.
  • Emulsion B (comparative emulsion)
  • the comparative emulsion B was prepared following the same preparation steps as for the comparative emulsion A hereinbefore, except for the addition of 1.175 g of copolymer TETRONIC 1508 ® from the start of the precipitation (thus adding the said copolymer before starting nucleation to the reaction vessel).
  • Emulsion C (inventive emulsion)
  • the inventive emulsion C was prepared following the same preparation steps as for the comparative emulsion A hereinbefore, except for the addition of 1.175 g of copolymer TETRONIC 1508 ® after the first growth step.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP98201093A 1998-04-07 1998-04-07 Emulsion sensible à la lumière ayant des grains tabulaires (100) riche en chlorure et procédé pour préparer les mêmes Withdrawn EP0949536A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP98201093A EP0949536A1 (fr) 1998-04-07 1998-04-07 Emulsion sensible à la lumière ayant des grains tabulaires (100) riche en chlorure et procédé pour préparer les mêmes
US09/256,239 US6136524A (en) 1998-04-07 1999-02-24 Light-sensitive emulsion having (100) tabular grains rich in silver chloride and method for preparing said grains
JP11097223A JP2000056419A (ja) 1998-04-07 1999-04-05 塩化銀に富む｛１００｝平板状粒子を有する感光性乳剤

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP98201093A EP0949536A1 (fr) 1998-04-07 1998-04-07 Emulsion sensible à la lumière ayant des grains tabulaires (100) riche en chlorure et procédé pour préparer les mêmes

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EP0949536A1 true EP0949536A1 (fr) 1999-10-13

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0518066A1 (fr) * 1991-05-14 1992-12-16 Eastman Kodak Company Elément radiographique à rendement de détection quantique amélioré
US5413904A (en) * 1994-03-18 1995-05-09 Eastman Kodak Company High chloride [100] tabular grain emulsions improved emulsions and improved precipitation processes
EP0762192A1 (fr) * 1995-08-16 1997-03-12 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
US5707793A (en) * 1995-04-19 1998-01-13 Fuji Photo Film Co., Ltd. Silver halide emulsion and silver halide photographic material using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0518066A1 (fr) * 1991-05-14 1992-12-16 Eastman Kodak Company Elément radiographique à rendement de détection quantique amélioré
US5413904A (en) * 1994-03-18 1995-05-09 Eastman Kodak Company High chloride [100] tabular grain emulsions improved emulsions and improved precipitation processes
EP0672940A2 (fr) * 1994-03-18 1995-09-20 Eastman Kodak Company Emulsions contenant des grains tabulaires (100) à haute teneur en chlorure: émulsions améliorées et procédés de précipitation améliorés
US5707793A (en) * 1995-04-19 1998-01-13 Fuji Photo Film Co., Ltd. Silver halide emulsion and silver halide photographic material using the same
EP0762192A1 (fr) * 1995-08-16 1997-03-12 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière

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