EP0017148A1 - Emulsions d'halogénure d'argent intérieurement dotées, riches en chlorures, procédés de fabrication de celles-ci et éléments photographiques - Google Patents

Emulsions d'halogénure d'argent intérieurement dotées, riches en chlorures, procédés de fabrication de celles-ci et éléments photographiques Download PDF

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EP0017148A1
EP0017148A1 EP80101580A EP80101580A EP0017148A1 EP 0017148 A1 EP0017148 A1 EP 0017148A1 EP 80101580 A EP80101580 A EP 80101580A EP 80101580 A EP80101580 A EP 80101580A EP 0017148 A1 EP0017148 A1 EP 0017148A1
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silver halide
silver
grains
emulsions
mole
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EP0017148B1 (fr
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Robert Earl Atwell
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Eastman Kodak Co
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Eastman Kodak Co
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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

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  • This invention is directed to improved photographic developing out high chloride silver halide emulsions, to methods of preparing such emulsions, and to photographic elements having coated thereon such emulsions.
  • high chloride silver halide emulsions and photographic elements of the developing out type offer distinct advantages in a number of respects.
  • silver chloride possesses less native sensitivity in the visible region of the spectrum than silver bromide, thereby permitting yellow filter layers to be omitted from multicolor photographic elements.
  • high chloride silver halides are more soluble than silver bromide and silver bromoiodide, thereby permitting development to be achieved in shorter times.
  • Unfortunately these advantages of high chloride silver halides have frequently not been realized in higher speed imaging applications, since the relatively higher speeds of silver bromide and silver bromoiodide have dictated their use.
  • silver halide emulsions of the developing out type comprised of silver halide grains which are at least 80 mole percent silver chloride and less than 5 mole percent silver iodide, based on total silver halide, characterized in that the silver halide grains are internally doped with cadmium, lead, copper, zinc or mixtures thereof in a speed increasing amount of up to 7 X 10 -5 mole per mole of silver halide. More generally 2 X 10 to 7 X 10 5 mole per mole of silver halide of the metal dopant is utilized.
  • the emulsions of the invention can be prepared by reacting a water soluble silver salt with a water soluble halide salt in an aqueous medium containing a peptizer to form radiation-sensitive silver halide grains.
  • the water soluble silver and halide salts are present in amounts so that silver halide grains are formed that are at least 80 mole percent silver chloride and less than 5 mole percent silver iodide.
  • Water soluble salts of cadmium, lead, copper, zinc or mixtures thereof are introduced into the aqueous reaction medium during formation of silver halide grains in amounts up to 7 X 10- 5 mole per mole of silver halide.
  • novel emulsions can be coated on photographic supports in the usual manner to prepare photographic elements.
  • the high chloride silver halide emulsions of the invention containing low concentrations of divalent metal ion dopants as described above exhibit increased photographic speeds.
  • such emulsions and photographic elements offer the art recognized advantages attributable to high chloride silver halide emulsions while achieving photographic speeds more commonly associated with silver bromide and silver bromoiodide photographic emulsions.
  • the fact that the inclusion of low concentrations of divalent metal ions of the type identified above can increase photographic speeds of these emulsions and photographic elements is surprising in view of the teachings in the art that low concentration levels of divalent metal ion dopants have the effect of desensitizing silver halide emulsions of higher bromide concentration to visible light (e.g.
  • the silver halide emulsions of the present invention are comprised of silver halide grains which are at least 80 mole percent silver chloride and less than 5 mole percent silver iodide, based on total silver halide.
  • the silver halide grains consist essentially of silver chloride. Because the solubility product constant of silver chloride is orders of magnitude higher than that of silver bromide or silver iodide, it is recognized that formation, ripening or extended holding of silver chloride grains in the presence of bromide and/or iodide ions will result in the inclusion of silver bromide and/or silver iodide in the silver chloride grains.
  • the silver halide grains are those which are at least 90 mole percent silver chloride.
  • the remaining silver halide, if any, present in the silver halide grains can be silver bromide, silver iodide or some combination of the two.
  • Silver bromide can be present in concentrations of up to 20 mole percent, preferably up to 15 mole percent, based on total silver halide.
  • Silver iodide is preferably present in concentrations less than 2 mole percent, based on total silver halide.
  • the high chloride silver halide grains contain a speed increasing amount of the metal dopant, cadmium, lead, copper, zinc or a combination of these elements in any proportion. While the metal dopants have the effect of increasing the sensitivity of surface chemically sensitized high chloride silver halide grains at concentrations up to 7 X 10 -5 mole per mole of silver halide, if the concentration levels are extended upwardly, the effect is to desensitize the emulsions. Significant improvements in the sensitivity of surface chemically sensitized emulsions have been observed when the metal dopants are introduced in concentrations in the range of from 2 X 10 to 7 X 10- 5 mole per mole of silver halide during formation of the high chloride silver halide grains.
  • cadmium, lead, zinc and copper internal dopants produce qualitatively similar effects in increasing the speed of surface chemically sensitized high chloride to silver halide emulsions, these elements differ in the degree to which they are capable of sensitizing the emulsions.
  • Cadmium produces emulsions of the highest attainable sensitivities followed in effectiveness by zinc, lead and copper in that order.
  • concentrations in the range of from 3 X 10 -6 to 5 X 10 -5 , optimally from 8 X 10 -6 to 2 X 10- 5 , mole per mole of silver halide during formation of the high chloride silver halide grains.
  • Radiation-sensitive silver halide emulsions are conventionally formed by reacting a water soluble silver salt with one or more water soluble halide salts in an aqueous medium containing a peptizer.
  • the choice and proportion of halide salts controls the halide content of the silver halide grains formed.
  • the peptizer maintains the silver halide grains in dispersion.
  • a metal dopant is intended to be introduced into the silver halide grains, it can be introduced in any convenient manner, typically separately or with one of the silver or halide salts or the peptizer, in the form of a salt which is water soluble in its contemplated concentration ranges.
  • emulsions containing the internally doped high chloride silver halide grains of the invention can be produced by otherwise conventional techniques, such as the double and single jet precipitation techniques described in U.S. Patents 2,950,972 and 3,901,711, and in U.K. Patent 1,121,496.
  • emulsions containing the internally doped high chloride silver halide grains of the invention can be formed by a double jet precipitation technique using accelerated flow rates to produce relatively monodispersed, cubic grains.
  • the term "monodispersed” indicates that at least 95 percent, by weight or by number, of the silver halide grains are within 40 percent of their mean effective diameter. In a specifically preferred form at least 95 percent, by weight or by number, of the silver halide grains are within 25 percent of the mean effective diameter, optimally within 10 percent of the mean effective diameter.
  • effective diameter is herein employed as the diameter of the circle corresponding in area to the area subtended by a silver halide grain as viewed through a microscope or in a photomicrograph. The measurement of silver halide grain sizes is discussed further in Mees and James, The Theory of the Photographic Process, 3rd Ed., Macmillan, 1966, pp. 36-43.
  • a silver salt such as silver nitrate, and a chloride salt, optionally employed in combination with a bromide and/or iodide salt, such as one or more chloride or other halide salts of an alkali or alkaline earth metal (e.g., sodium, potassium, magnesium or calcium), each in the form of an aqueous salt solution, are concurrently and separately introduced into the reaction vessel.
  • An aqueous dispersing medium is present in the reaction vessel prior to the introduction of the aqueous halide and silver salt solutions. The presence of the dispersing medium along with agitation, in most instances, facilitates uniform blending of the aqueous halide and silver salt solutions while avoiding localized concentration gradients.
  • a dispersing medium volume is initially present in the reaction vessel which is from about 10 to 90 percent, preferably 20 to 80 percent, that of the silver halide emulsion to be formed.
  • the dispersing medium is conventionally water or a dispersion of peptizer in water, optionally containing other ingredients, such as one or more silver halide ripening agents, more specifically described below.
  • peptizer in a concentration of at least 10 percent, most preferably 20 percent, of the total weight of the vehicle present in the finished emulsion is initially present in the dispersing medium within the reaction vessel. Where the peptizer is not initially entirely present in the dispersing medium, the balance of the peptizer is preferably added during addition of the silver and halide salts.
  • a minor portion of one of the silver or halide salt solutions is also initially present in the reaction vessel to adjust the pAg (log reciprocal silver ion concentration) of the reaction vessel contents at the outset of silver halide precipitation.
  • the dissolved silver salt reacts with dissolved halide salt to form silver halide crystals.
  • This initial phase of silver halide emulsion formation in which new silver halide crystals are being formed is referred to as nucleation.
  • additional silver halide formed as a reaction product can be precipitated onto these nuclei, causing the mean size of the silver halide to increase and ultimately resulting in silver halide grains of the desired mean effective diameter.
  • additional silver halide grain formation can occur after the initial formation of silver halide nuclei, by controlling the rate of addition of silver and halide salts continued silver halide precipitation onto the originally formed silver halide nuclei can be achieved.
  • This has the effect of producing a population of silver halide grains of similar size--i.e., monodispersed silver halide emulsions.
  • Techniques are known in the art which achieve shortened silver halide precipitation times by permitting accelerated rates of addition of silver and halide salts. Such techniques are disclosed, for example, in German OLS 2,107,118 and U.S. Patent 3,672,900.
  • Single jet silver halide grain precipitation is specifically contemplated as an alternative to double jet precipitation.
  • substantially the entire halide salt solution is present in the reaction vessel prior to introduction of the silver salt solution.
  • the silver halide grains which are formed are polydispersed--this is, they vary significantly in size and do not satisfy the grain size distribution requirements set forth above for monodispersed silver halide emulsions. Except for these differences, the preferred aspects of double jet silver halide precipitation techniques described above are also applicable to single jet precipitation techniques.
  • the metal dopant salts can be introduced into the reaction vessel after silver halide grain nuclei have been formed and before introduction of at least 85 percent, most preferably 75 percent, of the silver salt solution has been completed.
  • the divalent metal salts are preferably dissolved in water or other suitable solvent prior to addition to the reaction vessel.
  • the solution containing the divalent metal salt typically comprises from about 1 to 10 percent by weight of the dispersing medium of the emulsion, the proportions being merely a matter of choice and convenience.
  • the individual reactants can be added to the reaction vessel through surface or sub-surface delivery tubes by gravity feed or by delivery apparatus for maintaining control of the rate of delivery and the pH and/or pAg of the reaction vessel contents, as illustrated by U.S. Patents 3,821,002 and 3,031,304, and Claes et al, Photographische Korrespondenz, 102 Band, Number 10, 1967, p. 162.
  • specially contructed mixing devices can be employed, as illustrated by U.S. Patents 2,996,287; 3,342,605; 3,415,650 and 3,785,777; German OLS 2,556,885 and German OLS 2,555,364.
  • An enclosed reaction vessel can be employed to receive the mix reactants upstream of the main reaction vessel, as illustrated by U.S. Patents 3,897,935 and 3,790,386.
  • the initially formed silver halide grains i.e., silver halide nuclei
  • the initially formed silver halide grains are sufficiently small that they can be dispersed by water alone.
  • Peptizer can be added to the reaction vessel with the halide salt, the silver salt or both and/or independently of both.
  • peptizer concentrations from 0.2 to about 10 percent by weight, based on the total liquid or emulsion weight in the reaction vessel, can be employed, it is preferred to keep the concentration of the peptizer in the reaction vessel prior to and during silver halide formation below about 6 percent by weight, based on the total weight. It is common practice to maintain the concentration of the peptizer in the reaction vessel in the range of from about 2 to 6 percent, based on the total weight, prior to and during silver halide formation and to adjust the emulsion vehicle concentration upwardly for optimum coating characteristics by delayed, supplemental vehicle additions.
  • the emulsion as initially formed will contain from about 5 to 50 grams of peptizer per mole of silver halide, preferably about 10 to 30 grams of peptizer per mole of silver halide. Additional vehicle can be added later to bring the concentration up to as high as 300 grams per mole of silver halide. Preferably the concentration of vehicle in the finished emulsion is below 50 grams per mole of silver halide. When coated and dried in forming a photographic element the vehicle preferably forms about 30 to 70 percent by weight of-the emulsion layer.
  • Vehicles which include both binders and peptizers
  • Preferred peptizers are hydrophilic colloids, which can be employed alone or in combination with hydrophobic materials.
  • Suitable hydrophilic materials include both naturally occurring substances such as proteins, protein derivatives, cellulose derivatives--e.g., cellulose esters, gelatin --e.g., alkali-treated gelatin (cattle bone or hide gelatin) or acid-treated gelatin (pigskin gelatin), gelatin derivatives--e.g., acetylated gelatin, phthalated gelatin and the like, polysaccharides such as dextran, gum arabic, zein, casein, pectin, collagen derivatives, collodion, agar-agar, arrowroot, albumin and the like.
  • gelatin e.g., alkali-treated gelatin (cattle bone or hide gelatin) or acid-treated gelatin (pigskin gelatin), gelatin derivatives--e.g., acetylated gelatin, phthalated gelatin and the like, polysaccharides such as dextran, gum arabic, zein, casein, pectin, collagen derivatives,
  • materials commonly employed in combination with hydrophilic colloid peptizers as vehicles including vehicle extenders--e.g., materials in the form of latices include synthetic polymeric peptizers, carriers and/or binders such as poly(vinyl lactams), acrylamide polymers, polyvinyl alcohol and its derivatives, polyvinyl acetals, polymers of alkyl and sulfoalkyl acrylates and methacrylates, hydrolyzed polyvinyl acetates, polyamides, polyvinyl pyridine, acrylic acid polymers, maleic anhydride copolymers, polyalkylene oxides, methacrylamide copolymers, polyvinyl oxazolidinones, maleic acid copolymers, vinylamine copolymers, methacrylic acid copolymers, acryloyloxyalkylsulfonic acid copolymers, sulfoalkylacrylamide copolymers, poly- alkyleneimine copoly
  • vehicle materials including particularly the hydrophilic colloids, as well as the hydrophobic materials useful in combination therewith can be employed not only in the emulsion layers of the photographic elements of this invention, but also in other layers, such as overcoat layers, interlayers and layers positioned beneath the emulsion layers.
  • a silver halide ripening agent be present within the reaction vessel during silver halide formation.
  • the ripening agent can be entirely contained within the dispersing medium in the reaction vessel before silver and halide salt addition, or it can be introduced into the reaction vessel along with one or more of the halide salt, silver salt or peptizer.
  • the ripening agent can also be introduced independently during halide and silver salt additions.
  • Sulfur containing ripening agents are generally preferred.
  • Conventional thioether ripening agents such as those disclosed in U.S. Patent 3,271,157, can be employed.
  • Sufficient thioether ripening agent is employed to provide concentrations of from 0.05 to 50 grams, preferably about 0.1 to 20 grams, per mole of silver halide, based on the weight of silver.
  • Certain of the preferred organic thioether silver halide solvents can be represented by the formulas: and wherein: r and m are integers of 0 to 4; n is an integer of 1 to 4; p and q are integers of 0 to 3; X is an oxygen atom (-o-), a sulfur atom (-S-), a carbamyl radical a carbonyl radical or a carboxyl radical R and R' are ethylene oxide radicals (-O-CH 2 CH 2 -); Q and Z are hydroxy radicals (-OH), carboxy radicals, or alkoxy radicals (-0-alkyl) wherein the alkyl group has 1 to 5 carbon atoms; and Q and Z can also be substituents described for X linked to form a cyclic compound.
  • Preferred organic thioether silver halide ripening agents suitable for forming the emulsions of the invention include compounds represented by the formulas: and wherein: r is an integer of 1 to 3; s is an integer of 1 to 2; R 2 is an alkylene radical having 1 to 5 carbon atoms and is preferably ethylene (CH 2 CH 2 -); R 3 is an alkyl radical having 1 to 5 carbon atoms and is preferably ethyl; and R 4 is an alkylene radical having 1 to 5 carbon atoms and is preferably methylene (-CH 2 -).
  • thiocyanate salts can be used, such as alkali metal, most commonly potassium, and ammonium thiocyanate salts. While any conventional quantity of the thiocyanate salts can be introduced, preferred concentrations are generally from about 0.1 to 20 grams of thiocyanate salt per mole of silver halide, based on the weight of silver.
  • the emulsions of the invention containing high chloride silver halide grains are preferably washed or otherwise processed to remove soluble salts.
  • the soluble salts can be removed by chill setting and leaching, by coagulation washing, by centrifugation and decantation of a coagulated emulsion, by employing hydrocyclones alone or in combination with centrifuges, by diafiltration with a semipermeable membrane, or by employing an ion exchange resin.
  • the internally doped high chloride silver halide grains be surface chemically sensitized.
  • the high chloride silver halide grains can be surface chemically sensitized with active gelatin, as illustrated by T. H. James, The Theory of the Photographic Process, 4th Ed., Macmillan, 1977, pp. 67-76, or with sulfur, selenium, tellurium, platinum, palladium, iridium, osmium, rhenium or phosphorus sensitizers or combinations of these sensitizers, such as at pAg levels of from 5 to 10, pH levels of from 5 to 8 and temperatures of from 30 to 80°C, as illustrated by Research Disclosure, Vol.
  • Patents 3,891,446 and 3,984,249 by low pAg (e.g., less than 5) high pH (e.g., greater than 8) treatment or through the use of reducing agents, such as stannous chloride, thiourea dioxide, polyamines and amineboranes, as illustrated by U.S. Patent 2,983,609, Research Disclosure, Vol. 136, August 1975, Item 13654, U.S. Patents 2,518,698; 2,743,182; 3,026,203 and 3,361,564.
  • reducing agents such as stannous chloride, thiourea dioxide, polyamines and amineboranes
  • the internally doped high chloride silver halide grains are surface chemically sensitized with gold sensitizers employed alone or in combination with other conventional chemical sensitizers.
  • the internally doped high chloride silver halide grains can be surface gold sensitized with one or a combination of conventional gold sensitizers.
  • Illustrative gold sensitizers include gold hydroxide, gold chloride, potassium aurate, potassium auriaurite, potassium auricyanide, potassium aurithio- cyanate, gold sulfide, gold selenide, gold silver sulfide, gold iodide, potassium chloroaurate, ethylenediamine-bis-gold chloride and various organic gold sensitizers, as more fully described by U.S. Patents 2,642,361 and 3,297,447.
  • emulsions containing the high chloride silver halide grains can contain other components of a conventional nature.
  • Blending of silver halide emulsions is commonly undertaken to optimize characteristic curve shapes--e.g., adjust contrast, extended exposure latitude, increase maximum density and to achieve other, similar curve modifications.
  • Blends of surface-sensitive emulsions and internally fogged, internal image-forming emulsions can be employed, as illustrated by U.S. Patents 2,996,382; 3,397,987; 3,705,858 and 3,694,881, Research Disclosure, Vol.
  • the major portion, preferably essentially all, of the silver halide grains present in a silver halide emulsion or silver halide emulsion layer are internally doped high chloride silver halide grains substantially as described above.
  • the silver halide emulsion of the invention can be spectrally sensitized with dyes from a variety of classes, including the polymethine dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-,tetra- and poly-nuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyryls and streptocyanines.
  • the polymethine dye class which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-,tetra- and poly-nuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyryls and streptocyanines.
  • the cyanine spectral sensitizing dyes include, joined by a methine linkage, two basic heterocyclic nuclei, such as those derived from quinolinium, pyridinium, isoquinolinium, 3H-indolium, benz(e]-indolium, oxazolium, thiazolium, selenazolinium, imidazolium, benzothiazolium, benzoselenazolium, benzimidazolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium, thiazolinium dihydronaphthothiazolium, pyrylium and imidazopyrazinium quaternary salts.
  • two basic heterocyclic nuclei such as those derived from quinolinium, pyridinium, isoquinolinium, 3H-indolium, benz(e]-indolium, oxazolium, thiazol
  • the merocyanine spectral sensitizing dyes include, joined by a methine linkage, a basic heterocyclic nucleus of the cyanine dye type and an acidic nucleus, such as can be derived from barbituric acid, 2-thiobarbituric acid, rhodanine, hydantoin, 2-thiohydantoin, 4-thiohyantoin, 2-pyrazolin-5-one, 2-isoxazolin-5-one, indan-1,3-dione, cyclohexan-1,3-dione, 1,3-dioxan-4, 6-dione, pyrazolin-3,5-dione, pentan-2,4-dione, alkylsulfonyl acetonitrile, malononitrile, isoquinolin-4- one, and chroman-2,4-dione.
  • an acidic nucleus such as can be derived from barbituric acid, 2-thio
  • One or more spectral sensitizing dyes can be used. Dyes with sensitizing maxima at wavelengths throughout the visible spectrum and with a great variety of spectral sensitivity curve shapes are known. The choice and relative proportions of dyes depends upon the region of the spectrum to which sensitivity is desired and upon the shape of the spectral sensitivity curve desired. Dyes with overlapping spectral sensitivity curves will often yield in combination a curve in which the sensitivity at each wavelength in the area of overlap is approximately equal to the sum of the sensitivities of the individual dyes. Thus, it is possible to use combinations of dyes with different maxima to achieve a spectral sensitivity curve with a maximum intermediate to the sensitizing maxima of the individual dyes.
  • Combinations of spectral sensitizing dyes can be used which result in supersensitization--that is, spectral sensitization that is greater in some spectral region 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 achieved with selected combinations of spectra sensitizing dyes and other addenda, such as stabilizers and antifoggants, development accelerators or inhibitors, coating aids, brighteners and antistatic agents. Any one of several mechanisms as well as compounds which can be responsible for supersensitization are discussed by Gilman, Photographic Science and Engineering, Vol. 18, 1974, pp. 418-430.
  • Spectral sensitizing dyes also affect the emulsions in other ways. For example, many spectral sensitizing dyes either reduce (desensitize) or increase photographic speed within the spectral region of inherent sensitivity. Spectral sensitizing dyes can also function as antifoggants or stabilizers, development accelerators or inhibitors, reducing or nucleating agents, and halogen acceptors or electron acceptors, as disclosed in U.S. Patents 2,131,038; 3,501,310; 3,630,749; 3,718,470 and 3,930,860.
  • Sensitizing action can be correlated to the position of molecular energy levels of a dye with respect to ground state and conduction band energy levels of the silver halide crystals. These energy levels can in turn be correlated to polarographic oxidation and reduction potentials, as discussed in Photographic Science and Engineering, Vol. 18, 1974, pp. 49-53 (Sturmer et al), pp. 175-178 (Leubner) and pp. 475-485 (Gilman). Oxidation and reduction potentials can be measured as described by R. J. Cox, Photographic Sensitivity, Academic Press, 1973, Chapter 15.
  • Instability which increases minimum density in negative type emulsion coatings can be protected against by incorporation of stabilizers, antifoggants, antikinking agents, latent image stabilizers and similar addenda in the emulsion and contiguous layers prior to coating.
  • Most of the antifoggants which are effective in emulsions can also be used in developers and can be classified under a few general headings, as illustrated by C.E.K. Mees, The Theory of the Photographic Process, 2nd Ed., Macmillan, 1954, pp. 677-680.
  • the photographic elements prepared with the emulsions of the invention can be color photographic elements which form dye images through the selective destruction, formation or physical removal of dyes.
  • the photographic elements can produce dye images through the selective destruction of dyes or dye precursors, such as silver-dye-bleach processes.
  • the photographic elements can produce dye images through the selective formation of dyes, such as by reacting aromatic amine in its oxidized form with a dye-forming coupler.
  • the dye-forming couplers can be incorporated in the photographic elements.
  • the dye-forming couplers are chosen to form subtractive primary (i.e., yellow, magenta and cyan) image dyes and are nondiffusible, colorless couplers, such as two and four equivalent couplers of the open chain ketomethylene, pyrazolone, pyrazolotriazole, pyrazolobenzimidazole, phenol and naphthol type hydrophobically ballasted for incorporation in high-boiling organic (coupler) solvents.
  • subtractive primary i.e., yellow, magenta and cyan
  • nondiffusible, colorless couplers such as two and four equivalent couplers of the open chain ketomethylene, pyrazolone, pyrazolotriazole, pyrazolobenzimidazole, phenol and naphthol type hydrophobically ballasted for incorporation in high-boiling organic (coupler) solvents.
  • the dye-forming couplers upon coupling can release photographically useful fragments, such as development inhibitors or accelerators, bleach accelerators, developing agents, silver halide solvents, toners, hardeners, fogging agents, antifoggants, competing couplers, chemical or spectral sensitizers and desensitizers.
  • photographically useful fragments such as development inhibitors or accelerators, bleach accelerators, developing agents, silver halide solvents, toners, hardeners, fogging agents, antifoggants, competing couplers, chemical or spectral sensitizers and desensitizers.
  • the sensitizing dyes and other addenda incorporated into the layers of the photographic elements can be dissolved and added prior to coating either from water or organic solvent solutions, depending upon the solubility of the addenda. Ultrasound can be employed to dissolve addenda.
  • Semipermeable and ion exchange membranes can be used to introduce addenda, such as water soluble ions (e.g., chemical sensitizers).
  • Hydrophobic addenda particularly those which need not be absorbed to the silver halide grain surfaces to be; effective, such as couplers, redox dye-releasers and the like, can be mechanically dispersed directly, or in high boiling (coupler) solvents, or the hydrophobic addenda can be loaded into latices and dispersed, as illustrated by Chen Research Disclosure, Vol. 159, July 1977, Item 15930.
  • the layers can be applied to photographic supports by various procedures, including immersion or dip coating, roller coating, reverse roll coating, air knife coating, doctor blade coating, gravure coating, spray coating, extrusion coating, bead coating, stretch-flow coating and curtain coating.
  • the layers of the photographic elements can be coated on a variety of conventional photographic supports.
  • Typical photographic supports include polymeric film such as cellulose acetate and poly(ethylene terephthalate), wood fiber--e.g., paper, polyolefin- coated paper, metallic sheet and foil, glass and ceramic supporting elements provided with one or more subbing layers to enhance the adhesive, antistatic, dimensional, abrasive, hardness, frictional, antihalation and/or other properties of the support surface.
  • Photographic elements containing silver halide emulsions of this invention show particularly advantageous sensitivities when exposed to light.
  • the photographic elements are specifically contemplated for imagewise exposure under ordinary lighting conditions--that is, less than high intensity lighting conditions. Exposures can be monochromatic, orthochormatic or panchromatic. Imagewise exposures at ambient, elevated or reduced temperatures and/or pressures, continuous or intermittent exposures, exposure times ranging from minutes to relatively short durations in the millisecond to microsecond range and solarizing exposures, can be employed within the useful response ranges determined by conventional sensitometric techniques, as illustrated by T. H. James, The Theory of the Photographic Process, 4th Ed., Macmillan, 1977, Chapters 4, 6, 17, 18 and 23.
  • the high chloride silver halide grains form latent image sites at or near their surface, both in their primitive state and after surface chemical sensitization, unless the emulsions as described above are otherwise modified. Accordingly the emulsions can be processed in all conventional silver halide developers--including those containing sufficient silver halide solvent to reveal internal latent image sites, referred to in the art as surface and sub-surface developers, and those containing higher levels of silver halide solvents, referred to in the art as internal developers. It is accordingly apparent that the emulsions of the invention are useful for photographic applications requiring negative-working silver halide emulsions and photographic elements.
  • the light-sensitive silver halide contained in the photographic elements can be processed following exposure to form a visible image by associating the silver halide with an aqueous alkaline medium in the presence of a developing agent contained in the medium or the element.
  • Processing formulations and techniques are described in L. F. Mason, Photographic Processing Chemistry, Focal Press, London, 1966; Processing Chemicals and Formulas, Publication J-1, Eastman Kodak Company, 1973; Photo-Lab Index, Morgan and Morgan, Inc., Dobbs Ferry, New York, 1977, and Neblette's Handbook of Photography and Reprography - Materials, Processes and Systems, VanNostrand Reinhold Company, 7th Ed., 1977.
  • the photographic elements can be processed to form dye images which correspond to or are reversals of the silver halide rendered selectively developable by imagewise exposure.
  • Multicolor reversal dye images can be formed in photographic elements having differentially spectrally sensitized silver halide layers by black-and-white development followed by i) where the elements lack incorporated dye image formers, sequential reversal color development with developers containing dye image formers, such as color couplers, as illustrated by U.S. Patents 2,252,718; 2,950,970 and 3,547,650; ii) where the elements contain incorporated dye image formers, such as color couplers, a single color development step, as illustrated by the Kodak Ektachrome E4 and E6 and Agfa processes described in British Journal of Photography Annual, 1977, pp. 194-197, and Britihh Journal of Photography, August 2, 1974, pp. 668-669; and iii) where the photographic elements contain bleachable dyes, silver-dye-bleach processing, as illustrated by the Cibachrome P-10 and P-18 processes described in the British Journal of Photography Annual, 1977, pp. 209-212.
  • the photographic elements can be adapted for direct color reversal processing (i.e., production of reversal color images without prior black-and-white development), as illustrated by U.S. Patents 3,243,294, 3,647,452; 3,457,077 and 3,467,520; U.K. Patents 1,075,385 and 1,132,736; German Patents 1,259,700; and 1,257,570; 1,259,701 and German OLS 2,005,091.
  • Multicolor dye images which correspond to the silver halide rendered selectively developable by imagewise exposure can be produced by processing, as illustrated by the Koda- color C-22, the Kodak Flexicolor C-41 and the Agfa- color processes described in British Journal of Photography Annual, 1977, pp. 201-205.
  • the photographic elements can also be processed by the Kodak Ektaprint-3 and-300 processes as described in Kodak Color Dataguide, 5th Ed., 1975, pp. 18-19, and the Agfa color process as described in British Journal of Photography Annual, , 1977, pp. 205-206, such process being particularly suited to processing color print materials, such as resin-coated photographic papers, to form positive dye images.
  • the photographic elements can be processed in the presence of reducible species, such as transition metal ion complexes (e.g. cobalt(III) and ruthenium (III) complexes containing amine and/or amine ligands) and peroxy compounds (e.g. hydrogen peroxide and alkali metal perborates and percarbonates).
  • reducible species such as transition metal ion complexes (e.g. cobalt(III) and ruthenium (III) complexes containing amine and/or amine ligands) and peroxy compounds (e.g. hydrogen peroxide and alkali metal perborates and percarbonates).
  • Dye images can be formed or amplified by processes which employ in combination with a dye-image- generating reducing agent an inert transition metal ion complex oxidizing agent, as illustrated by U.S. Patents 3,748,138; 3,826,652; 3,862,842; 3,989,526 and 3,765,891; and/or a peroxide oxidizing agent, as illustrated by U.S. Patent 3,674,490, Research Disclosure, Vol. 116, December 1973, Item 11660, and Research Disclosure, Vol. 148, August 1976, Items 14836, 14846 and 14847.
  • the photographic elements can be particularly adapted to form dye images by such processes, as illustrated by U.S. Patents 3,822,129; 3,834,907; 3,902,905; 3,847,619 and 3,904,413.
  • transition metal ion complexes can accelerate silver halide development, as illustrated by U.S. Patents 3,748,138; 3,901,712 and 3,964,912; can bleach silver images, as illustratedby U.S. Patent 3,923,511; and can be employed to form tanned colloid images, as illustrated by U.S. Patents 3,856,524 and 3,862,855.
  • the peroxide oxidizing agents can be employed to form vesicular images, as illustrated by U.S. Patents 3,615,491; 3,765,890; and 3,776,730; U.K. Patents 1,329,444 and 1,332,693, Liebe et al and German OLS 2,420,521.
  • Image transfer systems include colloid transfer systems, as illustrated by U.S. Patents 2,596,756 and 2,716,059; silver salt diffusion transfer systems, as illustrated by U.S. Patents 2,352,014; 2,543,181; 3,020,155 and 2,861,885; imbibition transfer systems, as illustrated by U.S. Patent 2,882,156, and color image transfer systems, as illustrated by Research Disclosure, Vol. 151, November 1976, Item 15162, and Vol. 123, July 1974, Item 12331.
  • Color image transfer systems including emulsion layers,-receiving layers, timing layers, acid layers, processing compositions, supports and cover sheets
  • the images they produce can be varied by choosing among a variety of features, combinations of which can be used together as desired.
  • Film units can be chosen which are either integrally laminated or separated during exposure, processing and/or viewing, as illustrated by Canadian Patent 674,082; U.S. Patents 2,983,606; 3,445,228; 3,309,201; 2,543,181; 3,053,659; 3,415,644; 3,415,645 and 3,415,646; and U.K. Patent 1,330,524.
  • Positive-working chemistry can be chosen utilizing initially mobile dyes which are immobilized by development, as illustrated by U.S. Patents 2,983,606; 2 , 75 6, 1 4 2 ; 3,880,658; 3,854,945 and 3,839,035, or initially immobile dyes which are rendered mobile by development, as illustrated by U.K. Patent 1,464,104 and U.S. Patent 3,980,479; or negative-working imaging chemistry can be chosen utilizing the release of diffusible dyes from an immobile image dye-forming compound (e.g., a redox dye-releaser) as a function of development, as illustrated by Belgian Patent 838,062, Canadian Patent 602,607 and U.S.
  • an immobile image dye-forming compound e.g., a redox dye-releaser
  • An image to be viewed can be transferred from the image-forming layers.
  • a retained image can be formed for viewing as a concurrently formed complement -of the transferred image.
  • Positive transferred images and useful negative retained images can be formed when one of the imaging chemistry and the emulsion is negative-working and the other positive-working; and negative transferred images and positive retained images can be formed when both the imaging chemistry and the emulsion(s) are negative-working or positive-working.
  • the photographic elements can contain brighteners, absorbing and scattering materials, hardeners, coating aids, plasticizers and lubricants, antistatic layers, matting agents, developing agents and development modifiers as described in Paragraphs V, VIII, X, XI, XII, XIII, XVI, XX and XXI, of Research Disclosure, Vol. 176, December 1978, Item 17643. Still other conventional photographic features and applications not inconsistent with this invention will be readily apparent to those skilled in the art.
  • the photographic elements of this invention are intended to produce multicolor images which can be viewed in the elements or in a receiver when the elements form a part of a multicolor image transfer system.
  • at least three superimposed color-forming layer units are coated on a support.
  • Each of the layer units is comprised of at least one silver halide emulsion layer.
  • At least one of the silver halide emulsion layers preferably at least one of the silver halide emulsion layers in each color forming layer unit and most preferably each of the silver halide emulsion layers, contain an emulsion according to this invention as described herein.
  • the emulsion layers of one of the layer units are primarily responsive to the blue region of the spectrum, the emulsion layers of a second of the layer units are primarily responsive to the green region of the spectrum, and the emulsion layers of a third of the layer units are primarily responsive to the red. region of the spectrum. Since the high chloride silver halide emulsion exhibit only limited native sensitivity to the visible portion of the spectrum, the use of yellow filter dyes between adjacent layer units can be omitted in many instances and the layer units can be coated in any desired order.
  • the layer units each contain in the emulsion layers or in adjacent hydrophilic colloid layers at least one image dye providing compound. Incorporated dye-forming couplers and redox dye-releasers constitute exemplary preferred image dye providing means.
  • the blue, green and red responsive layer units preferably contain yellow, magenta and cyan image dye providing means, respectively.
  • the polydisperse silver chloride emulsions prepared as described above were coated, unsensitized and optimally gold sensitized, on a cellulose acetate film support at coverages of 6.90 g gelatin and 4.65 g Ag/m 2 .
  • the coated elements were then exposed through a graduated density step wedge, developed for 5 minutes in Kodak Developer DK-50, fixed, washed and dried.
  • the sensitometric results are set forth below in Table II.
  • a monodisperse silver chloride emulsion (1.5 ⁇ m) was prepared in the following manner:
  • a cadmium doped monodisperse silver chloride emulsion (1.5 ⁇ m) was prepared as described above (A), except that 10 mg of cadmium chloride (1.1 x 10- 5 mole/ Ag mole) were added to the reaction vessel prior to the start of the precipitation.
  • the monodisperse silver chloride emulsions prepared as described above (A and B) were optimally gold sensitized and coated and tested as described in Example 1.
  • the sensitometric results are set forth below in Table III.
  • a series of monodisperse silver chloride emulsions of approximately equal grain size (1.4-1.5 pm) were prepared by a method similar to that utilized in Example 2, except that varying amounts of cadmium chloride were added to the reaction vessel 5 minutes after the start of precipitation.
  • the resulting emulsions were then optimally gold sensitized, coated and processed as described in Example 1.
  • Table IV shows the concentrations of cadmium chloride utilized in the various emulsions. Relative speeds for these emulsions are shown in Curve A in Figure 1.
  • a series of monodisperse silver chloride emulsions were prepared by a method similar to that described in Example 2, except that varying amounts of lead chloride were added 5 minutes after the start of the precipitation.
  • the resulting emulsions were then optimally gold chemically sensitized and processed as described in Example 1.
  • Table V shows the concentrations of lead' chloride utilized. Relative speeds are shown in Curve B in Figure 1:
  • a series of monodisperse silver chloride emulsions were prepared by a method similar to that described in Example 2, except that the doped emulsions were prepared by adding 10 mg of either copper chloride or zinc chloride to the reaction vessel 5 minutes after the start of the precipitation.
  • the resulting emulsions were then optimally gold chemically sensitized, coated and processed as described in Example 1.
  • Table VI shows the concentration of the dopants utilized and the relative speeds are shown for the copper and zinc doped emulsions at points C and D, respectively, in Figure 1.
  • a silver chlorobromide emulsion (20 mole percent bromide) lacking an internal metal dopant was prepared in the following manner:
  • a silver chlorobromide emulsion (50 mole percent bromide) was prepared as in Paragraph A, except that the amounts of sodium chloride and potassium bromide utilized in the preparation of solution 2 were 279 g and 298 g, respectively.
  • a cadmium doped silver chlorobromide emulsion (50 mole percent bromide) was prepared as described in Paragraph C, except that the 10 mg of cadmium chloride (1.1 X 10 -5 mole/Ag mole) were added to the reaction vessel 5 minutes after the start of precipitation.
  • a plot is provided of the increase in relative speed versus the halide content.
  • the increase in relative speed is obtained by taking the relative speed of a photographic element formed with an undoped, surface chemically sensitized emulsion as 100 and plotting as an ordinate the additional speed of an otherwise identical element formed with an emulsion differing by containing a dopant, as described above.
  • the abscissa is plotted in terms of mole percent, the mole percent chloride in the silver halide emulsion being the numerator and the mole percent bromide in the silver halide emulsion being the denominator.
  • a series of six monodisperse silver chloroiodide emulsions were prepared in a manner similar to Example 2 except that a constant flow technique was utilized rather than an accelerated flow and the precipitation was carried out at a temperature of 60°C.
  • the emulsion series contains two silver chloroiodide emulsions (undoped and doped with 2 mg/Ag mole of cadmium chloride) at each of three separate chloride/ iodide ratios, 100/0, 98/2 and 96/4.
  • the emulsions having these chloride/iodide ratios were prepared by adding either 0, 16.6 or 33.2 g of potassium iodide, respectively, to solution 2 prior to precipitation.
  • the resulting emulsions were coated, exposed and processed by the method described in Example 1.
  • Figure 3 a plot is provided of the increase in relative speed achieved by doping versus the halide ratio.
  • Two incorporated coupler color print materials were prepared in the same manner, except differing in the emulsions utilized in the blue-sensitive, yellow dye-forming layer.
  • the multilayer coatings were prepared in the following manner:
  • the elements were identical, except for the emulsions utilized in the blue sensitized, yellow dye-releasing unit.
  • the elements were prepared as described below.
  • the quantities of components are stated as grams/meter 2 in parenthesis.
  • Silver halide quantities are given in terms of silver.
  • a poly(ethylene terephthalate) film support coated on one side with a carbon-pigmented gelatin layer was coated on the other side with the following layers:
  • the receiving element utilized comprised a paper support overcoated with a white-pigmented polyethylene layer, an acid layer comprising co-poly(styrene-maleic anhydride), a polymeric timing layer, a receiving layer comprising gelatin, 4-hydroxymethyl 4-methyl-l-phenyl-3-pyrazolidone, poly(N-vinylimidazole-co-3-hydroxyethyl-l-vinylimidazolium chloride) 90:10 weight ratio) and a gelatin overcoat layer.

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EP19800101580 1979-04-05 1980-03-26 Emulsions d'halogénure d'argent intérieurement dotées, riches en chlorures, procédés de fabrication de celles-ci et éléments photographiques Expired EP0017148B1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4766057A (en) * 1986-09-04 1988-08-23 Fuji Photo Film Co., Ltd. Method of forming a color image
US4912026A (en) * 1986-07-31 1990-03-27 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material feasible for rapid processing comprising high boiling solvent and gold compounds
EP0613044A2 (fr) * 1993-02-24 1994-08-31 Fuji Photo Film Co., Ltd. Matériau photographique contenant des grains à l'halogénure d'argent dopés au complexe cyano hexacoordoné

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0677131B2 (ja) * 1986-05-02 1994-09-28 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JPH0656474B2 (ja) * 1986-06-20 1994-07-27 富士写真フイルム株式会社 写真用ハロゲン化銀乳剤
JP2530470B2 (ja) * 1986-12-27 1996-09-04 コニカ株式会社 塩化銀を高含有率で含むハロゲン化銀カラ―写真感光材料
JPH04305644A (ja) * 1991-04-03 1992-10-28 Konica Corp ハロゲン化銀カラー写真感光材料

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GB121496A (en) * 1917-10-16 1918-12-16 Oil Extractors Ltd Improvements in or relating to Coal-distilling Apparatus.
US2950972A (en) * 1954-11-24 1960-08-30 Gen Aniline & Film Corp Photographic emulsions having increased sensitivity to x-ray and gamma ray radiation
DE2138873A1 (de) * 1970-08-03 1972-02-10 Eastman Kodak Co , Rochester, N Y (V St A) Verfahren zur Herstellung von direkt positiven photographischen Silberhalo gemdemulsionen
FR2209126A1 (fr) * 1972-12-04 1974-06-28 Eastman Kodak Co
US3901711A (en) * 1972-08-31 1975-08-26 Mitsubishi Paper Mills Ltd Silver halide photographic emulsion containing a gold salt and a polyalkylene oxide
DE2806855A1 (de) * 1977-02-18 1978-08-24 Eastman Kodak Co Photographische silberhalogenidemulsion

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JPS5816171B2 (ja) * 1976-03-17 1983-03-30 コニカ株式会社 リス型ハロゲン化銀写真感光材料
JPS54103017A (en) * 1978-01-31 1979-08-14 Mitsubishi Paper Mills Ltd Method of producing halogenated silver photographic emulsion
DE2951670C2 (de) * 1978-12-26 1986-09-18 E.I. Du Pont De Nemours And Co., Wilmington, Del. Fotografische Silberhalogenidgelatineemulsion, sowie ihre Herstellung und Verwendung

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Publication number Priority date Publication date Assignee Title
GB121496A (en) * 1917-10-16 1918-12-16 Oil Extractors Ltd Improvements in or relating to Coal-distilling Apparatus.
US2950972A (en) * 1954-11-24 1960-08-30 Gen Aniline & Film Corp Photographic emulsions having increased sensitivity to x-ray and gamma ray radiation
DE2138873A1 (de) * 1970-08-03 1972-02-10 Eastman Kodak Co , Rochester, N Y (V St A) Verfahren zur Herstellung von direkt positiven photographischen Silberhalo gemdemulsionen
US3901711A (en) * 1972-08-31 1975-08-26 Mitsubishi Paper Mills Ltd Silver halide photographic emulsion containing a gold salt and a polyalkylene oxide
FR2209126A1 (fr) * 1972-12-04 1974-06-28 Eastman Kodak Co
DE2806855A1 (de) * 1977-02-18 1978-08-24 Eastman Kodak Co Photographische silberhalogenidemulsion

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4912026A (en) * 1986-07-31 1990-03-27 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material feasible for rapid processing comprising high boiling solvent and gold compounds
US4766057A (en) * 1986-09-04 1988-08-23 Fuji Photo Film Co., Ltd. Method of forming a color image
EP0613044A2 (fr) * 1993-02-24 1994-08-31 Fuji Photo Film Co., Ltd. Matériau photographique contenant des grains à l'halogénure d'argent dopés au complexe cyano hexacoordoné
EP0613044A3 (fr) * 1993-02-24 1995-07-26 Fuji Photo Film Co Ltd Matériau photographique contenant des grains à l'halogénure d'argent dopés au complexe cyano hexacoordoné.

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CA1120765A (fr) 1982-03-30
EP0017148B1 (fr) 1982-12-08
JPS55135832A (en) 1980-10-23
JPH0219937B2 (fr) 1990-05-07

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