Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
• • 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
• • 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
  • G03C1/10—Organic substances
• • 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
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains

Definitions

• the invention relates to color photography. More specifically, the invention relates to color photographic elements that contain layer units that contain radiation-sensitive silver halide emulsions and produce dye images.
• silver halide emulsions are usually prepared by precipitating silver halide in the form of discrete grains (microcrystals) in an aqueous medium.
• An organic peptizer is incorporated in the aqueous medium to disperse the grains.
• Varied forms of hydrophilic colloids are known to be useful as peptizers, but the overwhelming majority of silver halide emulsions employ gelatino-peptizers.
• a summary of conventional peptizers, including gelatino-peptizers, is provided by Research Disclosure , Vol. 389, September 1996, Item 38957, II.
• Vehicles, vehicle extenders, vehicle-like addenda and vehicle related addenda A. Gelatin and hydrophilic colloid peptizers. Research Disclosure is published by Kenneth Mason Publications, Ltd., Dudley House, 12 North St., Emsworth, Hampshire P010 7DQ, England. The term "vehicle” includes both the peptizer used to disperse silver halide grains as they are being formed and the binder used in coating emulsion and processing solution penetrable layers of photographic elements. Gelatin and gelatin derivatives are commonly employed to perform the functions of both peptizer and binder.
• the characteristic that is primarily responsible for the dominance of silver halide photography is the image amplification capability of silver halide grains.
• incident photons are absorbed by the silver halide grains.
• an electron in the silver halide crystal lattice structure of a grain is promoted from a valence band energy level to a higher, conduction band energy level at which it is capable of migrating within the crystal lattice of the grain.
• conduction band energy level at which it is capable of migrating within the crystal lattice of the grain.
• a cluster of Ag° atoms is created, commonly referred to as a latent image site.
• the latent image site of a grain is capable of catalyzing the overall reduction of silver ions in the grain to Ag°, a huge amplification of the few original Ag + reductions to Ag° created by imagewise exposure.
• An imagewise exposed silver halide emulsion is brought into contact with a developer to produce a viewable image.
• a developer is an aqueous solution containing a developing agent, a reducing agent capable of selectively reducing latent image bearing silver halide grains to Ag°.
• the characteristic curve typically contains a portion that exhibits no change in density (minimum density or D min ) as a function of exposure transitioning with increased exposures to a portion in which density increases as a function of increased exposure, often resulting in a linear characteristic curve segment (i.e., ⁇ D/ ⁇ logE remains constant) transitioning with still higher exposures to a portion in which further exposure does not increase density (maximum density or D max ).
• Photographic element speeds we usually reported as differences in log E required to produce the same density in compared elements.
• Silver halide emulsions possess a native sensitivity to light having wavelengths ranging from the ultraviolet into the blue region of the visible spectrum.
• Spectral sensitizing dyes are adsorbed to the silver halide grain surfaces to extend sensitivity to longer wavelength portions of the spectrum.
• a summary of spectral sensitizing dyes is provided by Research Disclosure, Item 38957, cited above, V. Spectral sensitization and desensitization, A. Sensitizing Dyes.
• the function of a spectral sensitizer is to capture for latent image formation a photon of a wavelength the silver halide grain cannot itself capture.
• the FED sensitizer reduces recombination by donating an electron to fill the hole created by photon capture.
• fewer conduction band electrons return to hole sites in valence bands and more electrons are available to participate in latent image formation.
• the free radical is a single atom or compound that contains an unpaired valence shell electron and is for that reason highly unstable. If the oxidation potential of the free radical is equal to or more negative than -0.7 volt, the free radical immediately upon formation injects a second electron into the grain to eliminate its unpaired valence shell electron.
• the free radical also donates an electron to the grain
• absorption of a single photon in the grain has promoted an electron to the conduction band
• stimulated the FED sensitizer to donate an electron to file the hole left behind by the promoted electron, thereby reducing hole-electron recombination, and injected a second electron.
• the FED sensitizer contributes one or two electrons to the silver grain that contribute directly or indirectly to latent image formation.
• FED sensitizers and their utilization for increasing photographic speed are disclosed in Farid et al U.S. Patents 5,747,235 and 5,7547,236, and in the following commonly assigned filings: Lenhard et al EP 97200072.3, filed Oct. 30, 1996, and Gould et al EP 98936924.4, Farid et al EP 98202340.0, and Adin et al EP 98202347.5, each filed June 25, 1998.
• a tabular grain is one which has two parallel major faces that are clearly larger than any other crystal face and which has an aspect ratio of at least 2.
• the term "aspect ratio” is the ratio of the equivalent circular diameter (ECD) of the grain divided by its thickness (the distance separating the major faces).
• Tabular grain emulsions are those in which tabular grains account for greater than 50 percent of total grain projected area.
• Kofron et al U.S. Patent 4,439,520 illustrates the first chemically and spectrally sensitized high aspect ratio (average aspect ratio >8) tabular grain emulsions.
• tabular grain emulsions In their most commonly used form tabular grain emulsions contain tabular grains that have major faces lying in ⁇ 111 ⁇ crystal lattice planes and contain greater than 50 mole percent bromide, based on silver.
• a summary of tabular grain emulsions is contained in Research Disclosure, Item 38957, cited above, I. Emulsion grains and their preparation, B. Grain morphology, particularly sub-paragraphs (1) and (3).
• cationic starch as a peptizer for the precipitation of high bromide ⁇ 111 ⁇ tabular grain emulsions is taught by Maskasky U.S. Patents 5,604,085, 5,620,840, 5,667,955, 5,691,131, and 5,733,718.
• Oxidized cationic starches are advantageous in exhibiting lower levels of viscosity than gelatino-peptizers. This facilitates mixing. Under comparable levels of chemical sensitization higher photographic speeds can be realized using cationic starch peptizers. Alternatively, speeds equal to those obtained using gelatino-peptizers can be achieved at lower precipitation and/or sensitization temperatures, thereby avoiding unwanted grain ripening.
• black-and-white photographic image When silver halide is reduced to silver during development, the neutral density of the developed silver can be relied upon to create a black-and-white photographic image.
• Another imaging approach is to employ a primary amine color developing agent during development. The oxidized color developing agent is then reacted (coupled) with a dye image providing coupler to form an image dye. So-called "chromogenic" black-and-white images can be formed in which a combination of image dye forming couplers are employed to produce a black dye image which can be used in place of or in combination with developed silver to produce a black-and-white image.
• couplers which often do not form an image dye on coupling, can be relied upon for immediate or timed release of photographically useful fragments, such as development accelerators, development inhibitors, bleach accelerators, bleach inhibitors, developing agents (e.g., competing or auxiliary developing agents), silver complexing agents, fixing agents, toners, hardeners, tanning agents, antistain agents, stabilizers, antifoggants, competing couplers, and chemical or spectral sensitizers or desensitizers.
• development accelerators development inhibitors
• bleach accelerators bleach inhibitors
• developing agents e.g., competing or auxiliary developing agents
• silver complexing agents fixing agents, toners, hardeners, tanning agents, antistain agents, stabilizers, antifoggants, competing couplers, and chemical or spectral sensitizers or desensitizers.
• Couplers A summary of couplers is provided by Research Disclosure , Item 38957, cited above, X.
• Dye image formers and modifiers particularly B. Image-dye-forming couplers and C. Image dye modifiers.
• this invention is directed to a photographic recording element comprised of a support and at least one dye image forming layer unit containing (a) radiation-sensitive silver halide grains, (b) sensitizer for the silver halide grains, (c) peptizer for the silver halide grains, (d) at least one dye image providing coupler, and (e) at least one dye image enhancing coupler, wherein (a) the radiation-sensitive silver halide grains include tabular grains (1) having ⁇ 111 ⁇ major faces, (2) containing greater than 50 mole percent bromide, based on silver, and (3) accounting for greater than 50 percent total grain projected area, (b) the sensitizer includes a fragmentable electron donating sensitizer, (c) the peptizer is a water dispersible cationic starch, (d) the dye image providing coupler is a coupler capable of reacting with oxidized primary amine color developing agent to form a dye image, and (e) the dye image enhancing coupler is a coupler capable of reacting with oxid
• the present invention is generally applicable to color photographic elements that contain in at least one dye image forming layer unit a fragmentable electron donor (FED) sensitized, cationic starch peptized high bromide (111) tabular grain emulsion, a dye image providing coupler. and an electron transfer agent releasing (ETARC) coupler.
• FED fragmentable electron donor
• 111 high bromide tabular grain emulsions are those in which greater than 50 percent of total grain projected area is accounted for by tabular grains having (111) major faces and containing greater than 50 mole percent bromide, based on silver.
• starch Any conventional water dispersible cationic starch can be employed as a peptizer.
• starch is employed to include both natural starch and modified derivatives, such as dextrinated, hydrolyzed, alkylated, hydroxyalkylated, acetylated or fractionated starch.
• the starch can be of any origin, such as corn starch, wheat starch, potato starch, tapioca starch, sago starch, rice starch, waxy corn starch or high amylose corn starch.
• Starches are generally comprised oftwo structurally distinctive polysaccharides, u-amylose and amylopectin. Both are comprised of u-D-glucopyranose units. In u-arnylose the u-D-glucopyranose units form a 1,4-straight chain polymer. The repeating units tee the following form: In amylopectin, in addition to the 1,4-bonding of repeating units, 6-position chain branching (at the site of the -CH 2 OH group above) is also in evidence, resulting in a branched chain polymer. The repeating units of starch and cellulose are diasteroisomers that impart different overall geometries to the molecules.
• the ⁇ anomer found in starch and shown in formula I above, results in a polymer that is capable of crystallization and some degree of hydrogen bonding between repeating units in adjacent molecules, but not to the same degree as the ⁇ anomer repeating units of cellulose and cellulose derivatives.
• Polymer molecules formed by the ⁇ anomers show strong hydrogen bonding between adjacent molecules, resulting in clumps of polymer molecules and a much higher propensity for crystallization. Lacking the alignment of substituents that favors strong intermolecular bonding, found in cellulose repeating units, starch and starch derivatives are much more readily dispersed in water.
• the water dispersible starches employed in the practice of the invention are cationic--that is, they contain an overall net positive charge when dispersed in water.
• Starches are conventionally rendered cationic by attaching a cationic substituent to the ⁇ -D-glucopyranose units, usually by esterification or etherification at one or more free hydroxyl sites.
• Reactive cationogenic reagents typically include a primary, secondary or tertiary amino group (which can be subsequently protonated to a cationic form under the intended conditions of use) or a quaternary ammonium, sulfonium or phosphonium group.
• the cationic starch must be water dispersible. Many starches disperse in water upon heating to temperatures up to boiling for a short time (e.g., 5 to 30 minutes). High sheer mixing also facilitates starch dispersion. The presence of cationic substituents increases the polar character of the starch molecule and facilitates dispersion.
• the starch molecules preferably achieve at least a colloidal level of dispersion and ideally are dispersed at a molecular level-i.e., dissolved.
• oxidized cationic starch It is preferred to employ an oxidized cationic starch.
• the starch can be oxidized before (* patents above) or following the addition of cationic substituents. This is accomplished by treating the starch with a strong oxidizing agent. Both hypochlorite (ClO - ) or periodate (IO 4 - ) have been extensively used and investigated in the preparation of commercial starch derivatives and preferred. While any convenient oxidizing agent counter ion can be employed, preferred counter ions are those fully compatible with silver halide emulsion preparation, such as alkali and alkaline earth cations, most commonly sodium, potassium or calcium.
• the oxidation sites are usually at the 2 and 3 position carbon atoms forming the ⁇ -D-glucopyranose ring.
• the 2 and 3 position groups are commonly referred to as the glycol groups.
• the carbon-to-carbon bond between the glycol groups is replaced in the following manner: where R represents the atoms completing an aldehyde group or a carboxyl group.
• hypochlorite oxidation of starch is most extensively employed in commercial use.
• the hypochlorite is used in small quantities to modify impurities in starch. Any modification of the starch at these low levels is minimal, at most affecting only the polymer chain terminating aldehyde groups, rather than the ⁇ -D-glucopyranose repeating units themselves.
• the hypochlorite affects the 2, 3 and 6 positions, forming aldehyde groups at lower levels of oxidation and carboxyl groups at higher levels of oxidation.
• Oxidation is conducted at mildly acidic and alkaline pH (e.g., >5 to 11). The oxidation reaction is exothermic, requiring cooling of the reaction mixture. Temperatures of less than 45°C are preferably maintained. Using a hypobromite oxidizing agent is known to produce similar results as hypochlorite.
• hypochlorite oxidation is catalyzed by the presence of bromide ions. Since silver halide emulsions are conventionally precipitated in the presence of a stoichiometric excess of the halide to avoid inadvertent silver ion reduction (fogging), it is conventional practice to have bromide ions in the dispersing media of high bromide silver halide emulsions. Thus, it is specifically contemplated to add bromide ion to the starch prior to performing the oxidation step in the concentrations known to be useful in the high bromide ⁇ 111 ⁇ tabular grain emulsions--e.g., up to a pBr of 3.0.
• hypochlorite oxidation is normally carried out using a soluble salt, the free acid can alternatively be employed, as illustrated by M.E. McKillican and C.B. Purves, "Estimation of Carboxyl, Aldehyde and Ketone Groups in Hypochlorous Acid Oxystarches", Can. J. Chem. , Vol. 312-321(1954).
• Periodate oxidizing agents are of particular interest, since they are known to be highly selective.
• the periodate oxidizing agents produce starch dialdehydes by the reaction shown in the formula (II) above without significant oxidation at the site of the 6 position carbon atom. Unlike hypochlorite oxidation, periodate oxidation does not produce carboxyl groups and does not produce oxidation at the 6 position.
• Mchevretter U.S. Patent 3,251,826, the disclosure of which is here incorporated by reference, discloses the use of periodic acid to produce a starch dialdehyde which is subsequently modified to a cationic form. M Cambridgeretter also discloses for use as oxidizing agents the soluble salts of periodic acid and chlorine.
• one or more soluble salts may be released during the oxidation step.
• the soluble salts correspond to or are similar to those conventionally present during silver halide precipitation
• the soluble salts need not be separated from the oxidized starch prior to silver halide precipitation. It is, of course, possible to separate soluble salts from the oxidized cationic starch prior to precipitation using any conventional separation technique. For example, removal of halide ion in excess of that desired to be present during grain precipitation can be undertaken. Simply decanting solute and dissolved salts from oxidized cationic starch particles is a simple alternative. Washing under conditions that do not solubilize the oxidized cationic starch is another preferred option.
• the oxidized cationic starch is dispersed in a solute during oxidation, it can be separated using conventional ultrafiltration techniques, since there is a large molecular size separation between the oxidized cationic starch and soluble salt by-products of oxidation.
• the carboxyl groups formed by oxidation take the form -C(O)OH, but, if desired, the carboxyl groups can, by further treatment, take the form - C(O)OR', where R' represents the atoms forming a salt or ester. Any organic moiety added by esterification preferably contains from 1 to 6 carbon atoms and optimally from 1 to 3 carbon atoms.
• the minimum degree of oxidation contemplated is that required to reduce the viscosity of the starch. It is generally accepted (see citations above) that opening an ⁇ -D-glucopyranose ring in a starch molecule disrupts the helical configuration of the linear chain of repeating units which in turn reduces viscosity in solution. It is contemplated that at least one ⁇ -D-glucopyranose repeating unit per starch polymer, on average, be ring opened in the oxidation process. As few as two or three opened ⁇ -D-glucopyranose rings per polymer has a profound effect on the ability of the starch polymer to maintain a linear helical configuration. It is generally preferred that at least 1 percent of the glucopyranose rings be opened by oxidation.
• a preferred objective is to reduce the viscosity of the cationic starch by oxidation to less than four times (400 percent of) the viscosity of water at the starch concentrations employed in silver halide precipitation. Although this viscosity reduction objective can be achieved with much lower levels of oxidation, starch oxidations of up to 90 percent of the ⁇ -D-glucopyranose repeating units have been reported (Wurzburg, cited above, p. 29). A typical convenient range of oxidation ring-opens from 3 to 50 percent of the ⁇ -D-glucopyranose rings.
• the water dispersible cationic starch is present during the precipitation (during nucleation and grain growth or during grain growth) of the high bromide ⁇ 111 ⁇ tabular grains.
• precipitation is conducted by substituting the water dispersible cationic starch for all conventional gelatino-peptizers.
• the concentrations of the selected peptizer and the point or points of addition can correspond to those employed using gelatino-peptizers.
• emulsion precipitation can tolerate even higher concentrations of the selected peptizer.
• all of the selected peptizer required for the preparation of an emulsion through the step of chemical sensitization can be present in the reaction vessel prior to grain nucleation.
• This has the advantage that no peptizer additions need be interjected after tabular grain precipitation has commenced. It is generally preferred that from 1 to 500 grams (most preferably from 5 to 100 grams) of the selected peptizer per mole of silver to be precipitated be present in the reaction vessel prior to tabular grain nucleation.
• the high bromide ⁇ 111 ⁇ tabular grain emulsions that are formed preferably contain at least 70 (optimally at least 90) mole percent bromide, based on silver.
• Silver bromide, silver iodobromide, silver chlorobromide, silver iodochlorobromide, and silver chloroiodobromide tabular grain emulsions are specifically contemplated.
• silver chloride and silver bromide form tabular grains in all proportions, chloride is preferably present in concentrations of 30 mole percent, based on silver, or less. Iodide can be present in the tabular grains up to its solubility limit under the conditions selected for tabular grain precipitation.
• silver iodide can be incorporated into the tabular grains in concentrations ranging up to 40 mole percent, based on silver. It is generally preferred that the iodide concentration be less than 20 mole percent, based on silver. Typically the iodide concentration is less than 10 mole percent, based on silver. To facilitate rapid processing, such as commonly practiced in radiography, it is preferred that the iodide concentration be limited to less than 4 mole percent, based on silver. Significant photographic advantages can be realized with iodide concentrations as low as 0.5 mole percent, based on silver, with an iodide concentration of at least 1 mole percent, based on silver, being preferred.
• the high bromide ⁇ 111 ⁇ tabular grain emulsions can exhibit mean grain ECD's of any conventional value, ranging up to 10 ⁇ m, which is generally accepted as the maximum mean grain size compatible with photographic utility.
• the tabular grain emulsions of the invention typically exhibit a mean ECD in the range of from 0.2 to 7.0 ⁇ m.
• Tabular grain thicknesses typically range from 0.03 ⁇ m to 0.3 ⁇ m. For blue recording somewhat thicker grains, up to 0.5 ⁇ m, can be employed. For minus blue (red and/or green) recording, thin ( ⁇ 0.2 ⁇ m) tabular grains are preferred.
• tabular grains impart to emulsions generally increases as the average aspect ratio or tabularity of the tabular grain emulsions increases.
• aspect ratio ECD/t
• tabularity ECD/t 2 , where ECD and t are measured in ⁇ m
• the tabular grains having a thickness of less than 0.3 ⁇ m (preferably less than 0.2 ⁇ m and optimally less than 0.07 ⁇ m) and accounting for greater than 50 percent (preferably at least 70 percent and optimally at least 90 percent) of total grain projected area exhibit an average aspect ratio of greater than 5 and most preferably greater than 8.
• Tabular grain average aspect ratios can range up to 100, 200 or higher, but are typically in the range of from 12 to 80. Tabularities of >25 are generally preferred.
• silver salts can be epitaxially grown onto the tabular grains during the precipitation process. Epitaxial deposition onto the edges and/or corners of tabular grains is specifically taught by Maskasky U.S. Patent 4,435,501 and Daubendiek et al U.S. Patents 5,573,902 and 5,576,168, here incorporated by reference.
• the emulsions of the invention show sensitivity enhancements with or without epitaxy when chemically sensitized employing one or a combination of noble metal, middle chalcogen (sulfur, selenium and/or tellurium) and reduction chemical sensitization techniques.
• noble metal typically gold
• middle chalcogen typically sulfur
• reduction chemical sensitization techniques Conventional chemical sensitizations by these techniques are summarized in Research Disclosure , Item 38957, cited above, Section IV. Chemical sensitizations. It is preferred to employ at least one of noble metal (typically gold) and middle chalcogen (typically sulfur) and, most preferably, a combination of both in preparing the emulsions of the invention for photographic use.
• a cationic starch peptizer allows distinct advantages relating to chemical sensitization to be realized. Under comparable levels of chemical sensitization higher photographic speeds can be realized using cationic starch peptizers. When comparable photographic speeds are sought, a cationic starch peptizer in the absence of gelatin allows lower levels of chemical sensitizers to be employed and results in better incubation keeping. When chemical sensitizer levels remain unchanged, speeds equal to those obtained using gelatino-peptizers can be achieved at lower precipitation and/or sensitization temperatures, thereby avoiding unwanted grain ripening.
• emulsion washing can be combined with emulsion precipitation, using ultrafiltration during precipitation as taught by Mignot U.S. Patent 4,334,012.
• emulsion washing by diafiltration after precipitation and before chemical sensitization can be undertaken with a semipermeable membrane as illustrated by Research Disclosure, Vol. 102, October 1972, Item 10208, Hagemaier et al Research Disclosure , Vol.
• a specifically preferred approach to chemical sensitization employs a combination of sulfur containing ripening agents in combination with middle chalcogen (typically sulfur) and noble metal (typically gold) chemical sensitizers.
• Contemplated sulfur containing ripening agents include thioethers, such as the thioethers illustrated by McBride U.S. Patent 3,271,157, Jones U.S. Patent 3,574,628 and Rosencrants et al U.S. Patent 3,737,313.
• Preferred sulfur containing ripening agents are thiocyanates, illustrated by Nietz et al U.S. Patent 2,222,264, Lowe et al U.S. Patent 2,448,534 and Illingsworth U.S. Patent 3,320,069.
• middle chalcogen sensitizers are tetra-substituted middle chalcogen ureas of the type disclosed by Herz et al U.S. Patents 4,749,646 and 4,810,626, the disclosures of which are here incorporated by reference.
• Preferred compounds include those represented by the formula: wherein
• Preferred gold sensitizers are the gold(I) compounds disclosed by Deaton U.S. Patent 5,049,485, the disclosure of which is here incorporated by reference. These compounds include those represented by the formula: AuL 2 + X - or AuL(L 1 ) + X - wherein
• Preferred 2-[N-(2-alkynyl)amino]- meta -chalcoazoles can be represented by the formula: where
• the formula V compounds are generally effective (with the Vb form giving very large speed gains and exceptional latent image stability) when present during the heating step (finish) that results in chemical sensitization.
• the fragmentable electron donating sensitizer provides additional speed when used in place of one, some or all conventional chemical sensitizers or in combination with these sensitizers. It is common practice in chemically sensitizing gelatio-peptized emulsions to hold the emulsions for a period of time at an elevated temperature to effect chemical sensitization.
• the FED sensitizer can be added before heating when the sensitizer is sufficiently stable to withstand the elevated temperature without fragmenting. However, where a heating step is contemplated to effect a conventional chemical sensitization, it is preferred to add the FED sensitizer at the conclusion of the heating step.
• the oxidized cationic starch peptized emulsions can be efficiently chemically sensitized with conventional sensitizers, such as those of formulae (III), (IV) and (V) above, at lower temperatures.
• conventional sensitizers such as those of formulae (III), (IV) and (V) above
• chemical sensitization can be achieved at temperatures lower than those required for the sensitization of corresponding gelatino-peptized emulsions.
• the FED sensitizer can be added before, during or after addition of any other, conventional chemical sensitizers.
• Fragmentable electron donating (FED) sensitizers of the types disclosed by Farid et al U.S. Patents 5,747,235 and 5,7547,236; in Lenhard et al EP 97200072.3, filed Oct. 30, 1996; and in Gould et al EP 98936924.4, Farid et al EP 98202340.0, and Adin et al EP 98202347.5, each filed June 25, 1998; the disclosures of which are here incorporated by reference, are specifically contemplated for use in the practice of this invention.
• These FED sensitizers satisfy the formula X-Y', X-Y' forming the entire sensitizer or a moiety -X-Y' of the sensitizer, wherein
• a base, B - is covalently linked directly or indirectly to X.
• V oxidation potentials
• Electron elimination from compound X-Y occurs when the oxidation potential of X-Y is equal to or more negative than 1.4 volts. Electron elimination from the free radical X ⁇ occurs when X ⁇ exhibits an oxidation potential equal to or more negative than -0.7 volt.
• the structural features of X-Y are defined by the characteristics of the two parts, namely the fragment X and the fragment Y.
• the structural features of the fragment X determine the oxidation potential of the X-Y molecule and that of the radical X ⁇ , whereas both the X and Y fragments affect the fragmentation rate of the oxidized molecule X-Y ⁇ + .
• Y' is H
• the following represents the reactions believed to take place when the compound X-H undergoes oxidation and deprotonation to the base, B - , to produce a radical X ⁇ , which in a preferred embodiment undergoes further oxidation.
• Preferred X groups are of the general formula: The symbol "R" (that is R without a subscript) is used in all structural formulae in this patent application to represent a hydrogen atom or an unsubstituted or substituted alkyl group.
• ring represents a substituted or unsubstituted 5-, 6- or 7-membered unsaturated ring, preferably a heterocyclic ring.
• Preferred Y' groups are:
• Y' is -H, -COO - or - Si(R') 3 or -X'. Particularly preferred Y' groups are -H, -COO - or -Si(R') 3 .
• a base, B - is covalently linked directly or indirectly to X.
• the base is preferably the conjugate base of an acid of pKa between 1 and 8, preferably 2 to 7. Collections of pKa values are available (see, for example: Dissociation Constants of Organic Bases in Aqueous Solution, D. D. Peril (Butterworths, London, 1965); CRC Handbook of Chemistry and Physics , 77th ed, D. R. Lide (CRC Press, Boca Raton, F1, 1996)). Examples of useful bases are included in Table I.
• the fragmentable electron donating sensitizer contains a light absorbing group, Z, which is attached directly or indirectly to X, a silver halide absorptive group, A, directly or indirectly attached to X, or a chromophore forming group, Q, which is attached to X.
• Such fragmentable electron donating sensitizers are preferably of the following formulae: Z-(L-X-Y') k A-(L-X-Y') k (A-L) k -X-Y' Q-X-Y' A-(X-Y') k (A) k -X-Y' Z-(X-Y') k or (Z) k -X-Y'
• Preferred Z groups are derived from the following dyes:
• the linking group L may be attached to the dye at one (or more) of the heteroatoms, at one (or more) of the aromatic or heterocyclic rings, or at one (or more) of the atoms of the polymethine chain, at one (or more) of the heteroatoms, at one (or more) of the aromatic or heterocyclic rings, or at one (or more) of the atoms of the polymethine chain.
• the attachment of the L group is not specifically indicated in the generic structures.
• the silver halide adsorptive group A is preferably a silver-ion ligand moiety or a cationic surfactant moiety.
• A is selected from the group consisting of: i) sulfur acids and their Se and Te analogs, ii) nitrogen acids, iii) thioethers and their Se and Te analogs, iv) phosphines, v) thionamides, selenamides, and telluramides, and vi) carbon acids.
• Illustrative A groups include: and ⁇ CH 2 CH 2 -SH
• the point of attachment of the linking group L to the silver halide adsorptive group A will vary depending on the structure of the adsorptive group, and may be at one (or more) of the heteroatoms, at one (or more) of the aromatic or heterocyclic rings.
• the linkage group represented by L which connects the light absorbing group to the fragmentable electron donating group XY by a covalent bond is preferably an organic linking group containing a least one C, N, S, or O atom. It is also desired that the linking group not be completely aromatic or unsaturated, so that a pi-conjugation system cannot exist between the Z and XY moieties.
• the length of the linkage group can be limited to a single atom or can be much longer, for instance up to 30 atoms in length.
• a preferred length is from 2 to 20 atoms, and most preferred is 3 to 10 atoms.
• Q represents the atoms necessary to form a chromophore comprising an amidinium-ion, a carboxyl-ion or dipolar-amidic chromophoric system when conjugated with X-Y'.
• the chromophoric system is of the type generally found in cyanine, complex cyanine, hemicyanine, merocyanine, and complex merocyanine dyes as described in F.M. Hamer, The Cyanine Dyes and Related Compounds (Interscience Publishers, New York, 1964).
• Q groups include:
• Illustrative fragmentable electron donating sensitizers include:
• the FED sensitizer includes a dye chromophore, providing the photon capture capability of a spectral sensitizing dye and the additional electron injection capability of a FED sensitizer. This allows a dye chromophore containing FED sensitizer to be substituted for a conventional spectral sensitizing dye.
• Spectral sensitizing dyes of conventional types and in conventional amounts are contemplated for use with the FED sensitizers.
• a FED sensitizer containing a chromophore when employed in combination with one or more conventional spectral sensitizing dyes, can be chosen to absorb light in the same spectral region or a different spectral region than the conventional spectral sensitizing dye.
• spectral sensitizing dyes are provided by Research Disclosure, Item 38957, V. Spectral sensitization and desensitization, A. Sensitizing Dyes, cited above.
• spectral sensitizing dyes are adsorbed to the surfaces of the grains after chemical sensitization, but advantages for dye addition to high bromide ⁇ 111 ⁇ tabular grains prior to or during chemical sensitization have long been recognized, as illustrated by Kofron et al U.S. Patent 4,439,520.
• the FED sensitizer can be added to the emulsion prior to, during or following spectral sensitization.
• the FED sensitizer can be incorporated in the emulsion by the conventional techniques for dispersing spectral sensitizing dyes. That is, the FED sensitizer can be added directly to the emulsion or added after being dissolved in a solvent, such as water, methanol or ethanol, or a mixture of solvents (e.g., an aqueous alcoholic solution).
• a solvent such as water, methanol or ethanol, or a mixture of solvents (e.g., an aqueous alcoholic solution).
• the FED sensitizers may also be added from solutions containing base and/or surfactants.
• the FED sensitizers may also be incorporated in aqueous slurries or peptizer dispersions.
• FED sensitizers are added to the emulsions of the invention to allow intimate contact with the high bromide ⁇ 111 ⁇ tabular grains. In preferred forms the FED sensitizers are adsorbed to the grain surfaces.
• FED sensitizer concentrations in the emulsions of the invention can range from as low as 1 X 10 -8 mole per silver mole up to 0.1 mole per silver mole. A preferred concentration range is 5 X 10 -7 to 0.05 mole per silver mole. It is appreciated that the more active forms of the FED sensitizer (e.g., those capable of injecting a higher number of electrons per molecule) can be employed in lower concentrations while achieving the same advantageous effects as less active forms.
• the FED sensitizer be added to the emulsion of the invention before, during or immediately following the addition of other conventional incorporated sensitizers, increases in emulsion sensitivity have been observed even when FED sensitizer addition has been delayed until after the emulsion has been coated.
• the emulsions of the invention additionally preferably include one or more conventional antifoggants and stabilizers.
• conventional antifoggants and stabilizers are contained in Research Disclosure, Item 38957, VII. Antifoggants and stabilizers.
• a FED sensitizer in combination with a cationic starch peptizer results in somewhat higher minimum densities than when a gelatino-peptizer is substituted, even when conventional antifoggants and stabilizers are present in the emulsion. It has been discovered that this incremental increase in minimum density can be reduced or eliminated by treating the emulsion with an oxidizing agent during or subsequent to grain precipitation.
• Preferred oxidizing agents are those that in their reduced form have little or no impact on the performance properties of the emulsions in which they are incorporated.
• oxidizing agents such as hypochlorite (ClO - ) or periodate (IO 4 - ), are specifically contemplated.
• Specifically preferred oxidizing agents are halogen--e.g., bromine (Br 2 ) or iodine (I 2 ). When bromine or iodine is used as an oxidizing agent, the bromine or iodine is reduced to Br - or I - .
• bromine or iodine is used as an oxidizing agent, the bromine or iodine is reduced to Br - or I - .
• These halide ions can remain with other excess halide ions in the dispersing medium of the emulsion or be incorporated within the grains without adversely influencing photographic performance. Any level of oxidizing agent can be utilized that is effective in reducing minimum density.
• Concentrations of oxidizing agent added to the emulsion as low as 1 X 10 -6 mole per Ag mole are contemplated. Since very low levels of Ag° are responsible for increases in minimum density, no useful purpose is served by employing oxidizing agent concentrations of greater than 0.1 mole per Ag mole.
• a specifically preferred oxidizing agent range is from 1 X 10 -4 to 1 X 10 -2 mole per Ag mole.
• the silver basis is the total silver at the conclusion of precipitation of the high bromide ⁇ 111 ⁇ tabular grain emulsion, regardless of whether the oxidizing agent is added during or after precipitation.
• At least one dye image providing coupler and at least one electron transfer agent releasing (ETARC) coupler are present in the dye image forming layer unit.
• the term "coupler” is employed in its art recognized sense of denoting a compound that selectively reacts with oxidized (as opposed to non-oxidized) primary amine color developer agent during photographic element development.
• Dye image forming couplers complete a dye chromophore upon coupling.
• ETARC release an electron transfer agent.
• ETA electron transfer agent
• ETA is employed in its art recognized sense of denoting a silver halide developing agent that donates an electron (becomes oxidized) in reducing Ag + in silver halide to silver Ag° and is then regenerated to its original non-oxidized state by entering into a redox reaction with primary amine color developing agent.
• the color developing agent is oxidized and hence activated for coupling. Since ETA cycles between reactions with the silver halide grains and the color developing agent during development, it is not depleted during use, therefore very small amounts of ETA are highly effective.
• an ETARC satisfies the formula: COUP-(L) n -ETA wherein
• the electron transfer agent pyrazolidinone moieties are derived from compounds generally of the type described in U.S. Pat. Nos. 4, 209,580; 4,463,081; 4,471,045; and 4,481,287 and in published Japanese patent application Ser. No. 62-123,172.
• Such compounds comprise a 3-pyrazolidinone structure having an unsubstituted or a substituted aryl group in the 1-position.
• these compounds have one or more alkyl groups in the 4 or 5-positions of the pyrazolidinone ring.
• Preferred electron transfer agents suitable for use in this invention are represented by tautomeric structural formulas XI and XII: wherein:
• R 2 and R 3 groups are alkyl it is preferred that they comprise from 1 to 3 carbon atoms.
• R 2 and R 3 represent aryl, they are preferably phenyl.
• R 4 and R 5 are preferably hydrogen.
• R 6 represents sulfonamido
• it may be, for example, methanesulfonamido, ethanesulfonamido or toluenesulfonamido.
• a preferred amount of the ETARC in the image forming layer unit is 1.0 X 10 -3 to 1.0 mole per silver mole.
• a more preferred amount of the ETARC is 2.0 X 10 -2 to 5 X 10 -1 mole per silver mole, most preferably from 5 X 10 -2 to 4.0 X 10 -1 mole per silver mole.
• the ETARC is located in the image forming layer unit either in a silver halide emulsion layer or in a layer adjacent to the emulsion layer, preferably the former.
• releasable electron transfer agents suitable for use in this invention and falling within the above tautomeric structural formulas XI and XII (where R 1 , R 4 and R 5 are hydrogen), are presented in Table II: ETA No. R 2 R 3 R 6 1 -H -H -H 2 -CH 3 -H -H 3 -CH(CH 3 ) 2 -H -H 4 -CH 3 -CH 2 OH -H 5 -H -H p -CH 3 6 -H -H p -OCH 3 7 -CH 3 -CH 2 OH p -CH 3 8 -CH 3 -CH 2 OH p -OCH 3
• the ETA is attached to the coupler moiety at a position that will cause the ETA to be inactive until released.
• the point of attachment of the ETA to the coupler moiety COUP, or to the COUP-(L)n -linking moiety is that point where R 1 is attached after release.
• Such attachment inactivates the ETA moiety so that it is unlikely to cause undesirable reactions during storage of the photographic element.
• the oxidized developer formed in an imagewise manner as a consequence of silver halide development reacts with the COUP moiety to cleave the bond between COUP and L. Thereafter, subsequent reaction, not involving an oxidized developing agent, breaks the bond linking L and the blocked ETA to release the active ETA moiety.
• the -(L)- moiety comprises a divalent group by which it is attached to the ETA.
• a group can be or wherein
• linking group -(L) n - where it is present in the compounds described herein, is employed to provide for controlled release of the ETA pyrazolidinone moiety from the coupler moiety so that the effect of accelerated silver halide development can be quickly attained.
• linking groups can be used. These include quinonemethide linking groups such as are disclosed in U.S. Pat. No. 4,409,323; pyrazolonemethide linking groups such as are disclosed in U.S. Pat. No. 4,421,845; and intramolecular nucleophilic displacement type linking groups such as are disclosed in U.S. Pat. No. 4,248,962 and EPO 0 193 389 and 0 255 085.
• Typical useful linking groups include: wherein:
• the coupler moiety COUP can take the form of any conventional coupler moiety found in a coupler capable of releasing a photographically useful group (PUG).
• PUG releasing couplers are illustrated by U.S. Patents 3,148,062, 3,227,554, 3,617,291, 3,265,506, 3,632,345, and 3,660,095.
• the COUP moiety from which the electron transfer agent pyrazolidinone moiety is released, can be chosen from among conventional COUP moieties of image dye forming couplers, but the low quantities of ETARC required allow COUP moieties to be chosen that are found in couplers that do not produce image dye.
• the COUP moieties can be chosen to yield colorless products on reaction with oxidized color developing agents.
• the COUP moieties can alternatively form dyes which are unstable and which decompose into colorless products. Further, the COUP moieties can be chosen to provide dyes which wash out of the photographic recording materials during processing.
• the COUP moiety can be unballasted or ballasted with an oil-soluble or fat-tail group. It can be monomeric, or it can form part of a dimeric, oligomeric or polymeric coupler, in which case more than one ETA moiety or -(L) n -ETA moiety can be contained in the ETA releasing compound.
• COUP moieties Although many varied forms of COUP moieties are known, most COUP moieties have been synthesized to facilitate formation of image dyes having their main absorption in the red, green, or blue region of the visible spectrum.
• couplers which form cyan dyes upon reaction with oxidized color developing agents are described in such representative patents and publications as: U.S. Patents 2,772,162; 2,895,826; 3,002,836; 3,034,892; 2,474,293; 2,423,730; 2,367,531; 3,041,236; 4,333,999; and "Farbkuppler: Eine Literaturubersicht,” published in Agfa Mitannonen, Band III, pp. 156-175 (1961).
• the unsatisfied bond indicates the coupling position to which -(L) n -ETA may be attached.
• cyan dye-forming couplers are phenols and naphthols which form cyan dyes on reaction with oxidized color developing agent at the coupling position, i.e. the carbon atom in the 4-position of the phenol or naphthol.
• Preferred ETARC COUP moieties of the type found in cyan dye-forming couplers are: wherein R 9 and R 10 can represent a ballast group or a substituted or unsubstituted alkyl or aryl group, and R 11 represents one or more halogen (e.g. chloro, fluoro), alkyl having from 1 to 4 carbon atoms or alkoxy having from 1 to 4 carbon atoms.
• Couplers which form magenta dyes upon reaction with oxidized color developing agent are described in such representative patents and publications as: U.S. Patents 2,600,788; 2,369,489; 2,343,703; 2,311,082; 3,824,250; 3,615,502; 4,076,533; 3,152,896; 3,519,429; 3, 062,653; 2,908,573; 4,540,654; and "Farbkuppler: Eine Literaturubersicht,” published in Agfa Mitanderen, Band III, pp. 126-156 (1961).
• magenta dye-forming couplers are pyrazolones and pyrazolotriazoles which form magenta dyes upon reaction with oxidized color developing agents at the coupling position, i.e. the carbon atom in the 4-position for pyrazolones and the 7-position for pyrazolotriazoles.
• Preferred ETARC COUP moieties of the type found in magenta dye-forming couplers are: and wherein R 9 and R 10 are as defined above.
• R 10 for pyrazolone structures is typically phenyl or substituted phenyl, such as, for example, 2,4,6-trihalophenyl, and for the pyrazolotriazole structures R 10 is typically alkyl or aryl.
• Couplers which form yellow dyes upon reaction with oxidized color developing agent are described in such representative patents and publications as: U.S. Patents 2,875,057; 2,407,210; 3,265,506; 2,298,443; 3,048,194; 3, 447,928; and "Farbkuppler: Eine Literaturubersicht,” published in Agfa Mitannonen, Band III, pp. 112-126 (1961).
• yellow dye-forming couplers are acylacetamides, such as benzoylacetanilides and pivalylacetanilides. These couplers react with oxidized developer at the coupling position--i.e., the active methylene carbon atom.
• Preferred ETARC COUP moieties of the type found in yellow dye-forming couplers are: wherein R 9 and R 10 are as defined above and can also be hydrogen, alkoxy, alkoxycarbonyl, alkanesulfonyl, arenesulfonyl, aryloxycarbonyl, carbonamido, carbamoyl, sulfonamido, or sulfamoyl, and R 11 is hydrogen or one or more halogen, lower alkyl (e.g. methyl, ethyl), lower alkoxy (e.g., methoxy, ethoxy), or a ballast (e.g. alkoxy of 16 to 20 carbon atoms) group.
• R 9 and R 10 are as defined above and can also be hydrogen, alkoxy, alkoxycarbonyl, alkanesulfonyl, arenesulfonyl, aryloxycarbonyl, carbonamido, carbamoyl, sulfonamido
• Couplers which form colorless products upon reaction with oxidized color developing agent are described in such representative patents as: U.K. Specification 861,138 and U.S. Patents 3,632,345, 3,928,041, 3,958,993 and 3, 961,959.
• such couplers are cyclic carbonyl containing compounds which form colorless products on reaction with oxidized color developing agent and have the L group attached to the carbon atom in the ⁇ -position with respect to the carbonyl group.
• Preferred ETARC COUP moieties of the type found in couplers that produce colorless compounds on coupling are: wherein R 9 is as defined above, and r is 1 or 2.
• the reaction product of the coupler moiety and oxidized color developing agent can be: (1) colored and non-diffusible, in which case it will remain in the location of coupling; (2) colored and diffusible, in which case it may be removed from the photographic element during processing or allowed to migrate to from the location of coupling; or (3) colorless and diffusible or non-diffusible, in which case it will not contribute to image density.
• the groups R 9 and R 10 in the above structures can additionally be hydrogen when attached to an NH group or to a ring carbon atom.
• COUP-(L) n -ETA compounds include the following:
• ETARC couplers are provided by Michno et al U.S. Patent 4,859,578, Platt et al U.S. Patent 4,912,025 and Saito et al U.S. Patent 5,605,786, the disclosures of which are here incorporated by reference.
• the ETARC can itself form an image dye on coupling, in most instances the concentrations of the ETARC are less than those capable of providing a desired level of dye density in the absence of another image dye source. It is therefore contemplated to incorporate in the dye image forming layer unit a conventional image dye forming coupler in addition to the ETARC.
• the image dye forming coupler typically forms a cyan, magenta or yellow dye on coupling and can take the form of any of the conventional cyan, magenta or yellow image dye forming couplers disclosed in the patents cited above to show suitable COUP moieties for ETARC addenda that form a cyan, magenta or yellow image dye on coupling.
• Emulsion Layer Unit can consist of a single high bromide ⁇ 111 ⁇ tabular grain emulsion containing a cationic starch peptizer, a FED sensitizer, an ETARC and a dye image providing coupler as described above.
• the cationic starch peptizer added during emulsion precipitation typically forms only a small portion of the total vehicle of the emulsion layer.
• Additional cationic starch of the type used as a peptizer can be added to act as a binder.
• Patent 5,726,008 here incorporated by reference, describes a vehicle that can be chill set containing at least 45 percent by gelatin and at least 20 percent of a water dispersible starch. In addition to peptizer and binder, the vehicle is reacted with a hardener to increase its physical integrity as a coating and other addenda, such as latices, are also commonly incorporated.
• Conventional components which can be included within the vehicle of the emulsion layer summarized in Research Disclosure, Item 38957, II. Vehicles, vehicle extenders, vehicle-like addenda and vehicle related addenda and IX.
• Coating physical property modifying addenda--e.g., coating aids (such as surfactants), plasticizers and lubricants, matting agents and antistats are common vehicle components, conventional choices being illustrated by Research Disclosure , Item 38957, IX. Coating physical property modifying addenda.
• the Support can take the form of any conventional photographic element support.
• the Support is either transparent (e.g., a transparent film support) or a white reflective support (e.g., a photographic paper support).
• a listing of photographic element supports is provided in Research Disclosure, Item 38957, XV. Supports. In the majority of applications higher imaging speeds have been particularly sought for camera speed or "taking" films that have a transparent support.
• the film has a transparent support and forms a negative dye image
• the image bearing processed film is most commonly used as an exposure master for creating a viewable positive image in a print element (e.g., color paper).
• a transparent support and forms a positive dye image the image is most commonly viewed directly by protection.
• a taking film of increased speed can be realized by employing a reflective support. It is specifically contemplated to employ a support that is specularly reflective at the time of imagewise exposure, thereby increasing its imaging speed, but is converted to a transparent form during processing to facilitate conventional uses of taking films.
• Maskasky et al U.S. Patent 5,945,266, titled DYE IMAGE FORMING PHOTOGRAPHIC ELEMENT AND PROCESSING TO PRODUCE A VIEWABLE IMAGE commonly assigned to discloses employing a transparent film support bearing a silver mirror coating that is capable of removal during photographic processing.
• Elements IIa and IIb illustrate common photographic element constructions useful for chromogenic black-and-white imaging or producing a single color dye image.
• the Support can take any of the forms described above--i.e., any conventional form.
• the Antihalation Layer is interposed between the Support and the Emulsion Layer Unit.
• the Antihalation Layer can be moved to be back side of the Support, as shown in Element IIb, and becomes the Pelloid Layer.
• the Pelloid Layer also acts as both an antihalation layer and an anti-curl layer.
• the Antihalation Layer and Pelloid Layer each contain one or more dyes capable of being rendered colorless (i.e., discharged) during photographic processing. Dyes of this type are listed in Research Disclosure, Item 38957, VII. Absorbing and scattering materials, B. Absorbing materials and C. Discharge.
• the Protective Overcoat is provided to protect the Emulsion Layer Unit.
• Each of the Antihalation Layer, Pelloid Layer and Protective Overcoat contain a vehicle.
• the vehicle is comprised of binder, hardener, and selections of the remaining components of the emulsion layer described above.
• the surface layers, the Pelloid Layer and the Protective Overcoat are particularly preferred locations for surface modifying addenda, such as lubricants, matting agents and antistats.
• the Protective Overcoat is also a preferred location for the incorporation of UV stabilizers, a summary disclosure of which is provided in Research Disclosure, Vol. 370, February 1995, Item 37038, X. UV Stabilizers.
• the Magnetic Imaging Layer is an optional, but preferred layer having as its purpose to store information about the photographic element for use in exposure or subsequent processing. Magnetic imaging layers are illustrated by Research Disclosure , Item 38957, XIV. Scan facilitating features and James U.S. Patents 5,254,441 and 5,254,449.
• Emulsion Layer Unit can consist of a single emulsion layer, it is recognized that the Emulsion Layer Unit can contain a blend of invention emulsions or a blend of one or more invention emulsions and one or more conventional emulsions. It is also common practice to divide emulsion layer units into two or three separate emulsion layers, differing in imaging speed.
• Emulsion Layer Unit By forming the Emulsion Layer Unit of a faster emulsion layer and a slower emulsion layer, with the faster emulsion layer positioned to receive exposing radiation (i.e., positioned farther from the support) first, a higher speed is realized than when the faster and slower emulsions are blended in a single layer.
• the slower emulsion layer When the slower emulsion layer is positioned to first receive exposing radiation, a higher contrast is realized than when the faster and slower emulsions are blended and coated in a single layer.
• the third emulsion layer is interposed between the faster and slower emulsions and is chosen to exhibit an intermediate speed. The function of the third emulsion layer is to allow longer exposure latitudes to be realized. Chang and Friday U.S. Patents 5,314,793 and 5,360,703, here incorporated by reference, disclose emulsion layer units containing three emulsion layers differing in speed to provide a useful exposure latitude of greater than 1.0 log
• the invention emulsion When one or more other emulsions are employed in combination with an emulsion satisfying the grain, peptizer and coupler requirements of the invention (hereinafter referred to as the invention emulsion), they can be chosen from among conventional negative-working radiation-sensitive silver halide emulsions, such as those described in Research Disclosure , Item 38957, I. Emulsion grains and their preparation, with paragraph E. Blends, layers and performance categories, further illustrating emulsion combinations. When one or more conventional emulsions are employed in combination with one or more invention emulsions, the invention emulsions are preferred choices for higher speeds, since they exhibit unexpectedly high speeds.
• a conventional emulsion is present in an Emulsion Layer Unit with an invention emulsion, it is preferably also a high (>50 mole percent, based on silver) bromide emulsion, and it is in most instances also a tabular grain emulsion.
• the photographic elements of the invention can rely on a combination of developed silver and image dye to produce a viewable image.
• Application of the invention to chromogenic black-and-white imaging is specifically contemplated.
• Elements I, IIa and IIb can be employed to form a positive dye image.
• Positive dye images are preferably formed by color reversal processing--that is, development of the imagewise exposed element without dye formation followed by a second, dye image forming development step in which residual silver halide not developed in the first development step is developed.
• Color reversal processing and element features particularly contemplated for photographic elements intended for color reversal processing are summarized in Research Disclosure , Item 38957, XIII. Features applicable only to color positive, B. Color reversal, and XVIII. Chemical development systems, B. Color-specific processing systems, paragraph (1).
• the photographic elements of the invention produce negative dye images.
• Color negative processing and element features particularly contemplated for photographic elements intended for color reversal processing are summarized in Research Disclosure , Item 38957, XII. Features applicable only to color negative and XVIII. Chemical development systems, B. Color-specific processing systems, paragraphs (3) through (10).
• a color developing agent is a reducing agent that, upon oxidation is capable of reacting with a conventional image dye forming coupler to produce a dye.
• Color developing agents include a primary amine group, typically attached to a phenyl ring.
• Preferred color developing agents are p -phenylenediamines, particularly the N,N-dialkyl- p -phenylenediamines. Further illustrations of color developing agents are provided by Research Disclosure , Item 38957, XIX. Development, A. Developing agents and James The Theory of the Photographic Process , 4th Ed., Macmillan, New York, 1977, Chapter 12 Principles and Chemistry of Color Photography, III. Color Forming Agents, A. Color Developers.
• a full color recording photographic element that is, an element capable of recording sufficient image information to allow the image and colors of the photographic subject to be reproduced, either within the color recording photographic element itself or in another color recording photographic element:
• the Support and the 1 st , 2 nd and 3 rd Color Recording Layer Units are essential components for all color recording applications. The remaining components are either optional or required only in specific applications.
• the Protective Overcoat, Transparent Film Support, Pelloid and Magnetic Imaging Layer have been described above and require no further comment.
• Each of the Recording Layer Units is an Emulsion Layer Unit constructed of the components described above, except as noted below, that has been chosen to be responsive to one of the blue, green and red portions of the visible spectrum.
• At least one invention emulsion is present in at least one and preferably each of the Recording Layer Units. Any one of the following layer unit sequences is possible:
• Each of the blue, green and red recording layer units preferably contains a dye image providing compound that produces a dye image of a different hue.
• the blue, green and red recording layer units are constructed to produce yellow, magenta and cyan dye images, respectively.
• the Blue Recording Layer Unit contains a yellow dye-forming coupler
• the Green Recording Layer Unit contains a magenta dye-forming coupler
• the Red Recording Layer Unit contains a cyan dye-forming coupler.
• conventional image dye modifiers can be incorporated in the Recording Layer Unit, such as those described in Research Disclosure , Item 38957, X. Dye image formers and modifiers, C. Image dye modifiers and D. Hue modifiers/stabilization.
• the 1 st and 2 nd Interlayers and the Undercoat can contain the same selections of vehicles as described above.
• the Undercoat can be replaced by the Antihalation Layer described above allowing the Pelloid can be omitted.
• the 1 st and 2 nd Interlayers preferably contain oxidized developing agent scavengers to prevent color developing agent oxidized in one layer unit from migrating to an adjacent layer unit.
• Typical oxidized developing agent scavengers include ballasted (i.e., immobilized) hydroquinone and aminophenol developing agents.
• Patent 5,434,038 discloses a color negative film containing a masking coupler that is equally suited for image retrieval by printing or scanning.
• Color recording photographic element constructions specifically adapted for the scan retrieval of image information are illustrated by Research Disclosure , Item 38957, XIV. Scan facilitating features, Paragraph (1).
• the disclosures of the following more recently issued patents of color recording photographic element constructions particularly adapted for scan image retrieval are here incorporated by reference: Sutton et al U.S. Patents 5,300,413 and 5,334,469, Sutton U.S. Patents 5,314,794 and 5,389,506, Evans et al U.S. Patent 5,389,503, Simons et al U.S. Patent 5,391,443, Simons U.S. Patent 5,418,119 and Gasper et al U.S. Patent 5,420,003.
• Full color recording photographic elements are typically employed to record exposures over the full range of the visible spectrum. Occasionally color recording photographic elements are employed to record also exposures in the near ultraviolet and/or near infrared portions of the spectrum. When this is undertaken, an additional layer unit can be provided for this purpose.
• Exposure measured in lux-seconds
• I exposure intensity
• ti time of exposure
• Common photographic applications span exposures ranging from 10 -5 to 10 3 seconds, and even relatively inexpensive cameras can accommodate exposures ranging from 10 -3 to 10 2 seconds.
• reciprocity all combinations of varied exposure times and varied exposure intensities that produce the same product (i.e., the same exposure) result in the same image density.
• the performance of photographic elements shows varying levels of departure from the law of reciprocity, commonly referred to as reciprocity failure.
• Exposure of camera speed color recording photographic elements in limited use and recyclable cameras is specifically contemplated. Limited use camera and incorporated film constructions are the specific subject matter of Item 338957, Section XVI Exposure, cited above, paragraph (2).
• This example has as its purpose to demonstrate the advantage in speed demonstrated by a FED sensitized cationic starch peptized high bromide ⁇ 111 ⁇ tabular grain emulsion as compared to a similarly prepared emulsion, but prepared using a gelatino-peptizer.
• Emulsion S1 (example)
• a starch solution was prepared by heating at 85°C for 45 min a stirred mixture of 8L distilled water and 160 g of an oxidized cationic waxy corn starch.
• the starch derivative, STA-LOK® 140 is 100% amylopectin that had been treated to contain quaternary ammonium groups and oxidized with 2 wt % chlorine bleach. It contains 0.31 wt % nitrogen and 0.00 wt % phosphorous. It was obtained from A. E.
• the resulting tabular grain emulsion was washed by ultrafiltration at 40°C to a pBr of 3.26. Then 27 g of bone gelatin (methionine content ⁇ 55 micromole per g gelatin) per mole silver was added.
• the ⁇ 111 ⁇ tabular grains had an average equivalent circular diameter of 3.8 ⁇ m, an average thickness of 0.07 ⁇ m, and an average aspect ratio of 54.
• the tabular grain population made up 99% of the total projected area of the emulsion grains.
• Emulsion G1 (control)
• the AgNO 3 solution was added at 1.0 mL per min for 1 min then accelerated to 25 mL per min in 150 min and held at this flow rate until a total of 2,453 mL of the AgNO 3 solution was used.
• the salt solution was concurrently added until 240 mL of the AgNO 3 solution had been added, then a new salt solution of 2.5 M NaBr, 0.04 M KI to which 0.45 g per L of bromine was added was used to maintain a pBr of 1.44 throughout the rest of the precipitation.
• the total making time of the emulsion was 194 min.
• the emulsion was cooled to 40°C and ultrafiltered to a pBr of 3.26. Then 12.4 g per mole silver of bone gelatin (methionine content ⁇ 55 micromole per g gelatin) was added.
• the resulting tabular grain emulsion was similar to Emulsion S1 in the measured grain parameters of average ECD, thickness, and proportion of tabular grains as a percentage of total grain projected area.
• Epitaxy was deposited on the grains of each of Emulsions S1 and G1 by the following procedure: A vigorously stirred 1.0 mole aliquot of the emulsion was adjusted to a pAg of 7.59 at 40°C by the addition of 0.25 M AgNO 3 solution. Then 5 mL of a 1M KI solution was added followed by 11 mL of a 3.77 M NaCl solution.
• the blue spectral sensitizing dye anhydro-5,5'-dichloro-3,3'-bis(3-sulfopropyl)thiacyanine hydroxide, triethylammonium salt
• the blue spectral sensitizing dye anhydro-5,5'-dichloro-3,3'-bis(3-sulfopropyl)thiacyanine hydroxide, triethylammonium salt
• Electron microscopy analysis of the resulting emulsions showed the tabular grains had epitaxial deposits located primarily at the tabular grain corners and edges. As formulated these deposits had a nominal halide composition of 42 M% chloride, 42 M% bromide, and 16 M% iodide, based on silver.
• the emulsions were then heated at 50°C for 10 minutes, cooled to 40°C, then sequentially 1-(3-acetamidophenyl)-5-mercaptotetrazole (0.489 mmole), FED 2 (2.8 micromole), and 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene (10 mmole ) were added.
• each of sensitized Emulsions 1S and 1G were coated on clear acetate support having an antihalation layer on the opposite side.
• the coatings had laydowns of 1.08 g/m 2 silver, 1.62 g/m 2 yellow dye-forming coupler, 3.2 g/m 2 gelatin and surfactant.
• a solution of gelatin and bis(vinylsulfonylmethyl)ether were overcoated at 0.9 g/m 2 gelatin and 72 mg/ m 2 hardener, respectively.
• Each of the film coatings were exposed for 0.01 sec to a 5500 K color temperature tungsten light source filtered through a Kodak Wratten TM 2B filter and a 0 to 4 density step tablet. The exposed film coatings were processed using the Kodak Flexicolor TM C-41 color negative film process.
• Example 1 the large speed advantage of Emulsion S1 over Emulsion G1 is in part attributable to the known speed advantage for substituting a cationic starch peptizer for gelatin and in part unexpected.
• This example has as its purpose to ascertain the extent of the speed advantage that results from substituting cationic starch peptizer for gelatino-peptizer, with no FED sensitizer present.
• Emulsions S1 and G1 were remade as Emulsions S2 and G2 with these modifications: The FED sensitizer was omitted and the bromine oxidizing agent used to control elevated fog generated by FED sensitizer was also omitted. Repeating the performance comparison of Example 1, the following performance characteristics were noted: Emulsion D min Gamma Speed S2(no FED) 0.11 1.85 107 G2(no FED) 0.10 1.71 100
• This example has as its purpose to demonstrate the advantage in minimum density attributable to the presence of the oxidizing agent during grain precipitation in Emulsion S1.
• Emulsion S3 An emulsion satisfying the requirements of the invention, Emulsion S3, was precipitated similarly as Emulsion S1, except that the bromine oxidizing agent added during precipitation was omitted. In all other respects Example 1 was repeated. The reported grain parameters of Emulsions S1 and S3 were similar. The performance of Emulsions S1, G1 and S2 are compared in Table V. Emulsion D min Gamma Speed S1 (example) 0.13 1.80 130 G1 (control) 0.10 1.97 106 S3 (example) 0.21 1.80 126
• This example has as its purpose to demonstrate that delaying oxidizing agent addition until after precipitation is effective.
• Example 1 was repeated as applied to Emulsion S1, but with the difference that bromine was absent from the emulsion during precipitation, but was added subsequent to precipitation by the following procedure:
• Example Emulsion S4 was prepared similarly to that of Emulsion S1, except that no bromine was used before or during the precipitation. After the precipitation was complete, 28 mL of saturated bromine water ( ⁇ 0.013 mole) was added to the stirred emulsion at 40°C maintaining the pH at 5.0 with dilute NaOH solution. (The reaction was over within 2 min after the bromine water addition, as indicated by the amount of NaOH that was needed to maintain the pH at 5.0.) The emulsion was ultrafiltered.
• Example Emulsions S1 and S4 were identical.
• the performance of Emulsions S1, S3 and S4 are compared in Table VI.
• Emulsion D min Gamma Speed S1 (pptn Br) 0.13 1.80 130 S3 (no Br) 0.21 1.80 126 S4 (post pptn Br) 0.16 1.69 130
• This example has as its purpose to demonstrate the further, unexpected increase in the speed advantage demonstrated by FED sensitized cationic starch peptized high bromide ⁇ 111 ⁇ tabular grain emulsion over a FED sensitized gelatin peptized high bromide ⁇ 111 ⁇ tabular grain emulsion when an ETARC is added to the emulsion containing imaging layer unit of the photographic element.
• the total making time of the emulsion was 194 min.
• the longer making time of this emulsion as compared to Emulsion S5 is attributed to the greater grain growth restraining action of the gelatino-peptizer as compared to the cationic starch peptizer.
• the emulsion was cooled to 40°C and ultrafiltered to a pBr of 3.26. Then 12.4 g per mole silver of bone gelatin (methionine content ⁇ 55 micromole per g gelatin) was added.
• the resulting tabular grain emulsion was similar to Emulsion S5 in the measured grain parameters of average ECD, thickness, and proportion of tabular grains as a percentage of total grain projected area.
• Each of sensitized Emulsions S5 and G5 were coated on clear acetate support having an antihalation layer on the opposite side. Two coatings were prepared containing each emulsion, one coating containing an ETARC coupler and the other lacking an ETARC coupler.
• the coatings lacking an ETARC coupler were prepared as follows:
• the emulsion coated layer contained 0.81 g/m 2 silver, 0.324 g/m 2 cyan dye-forming coupler, 4.32 g/m 2 gelatin and surfactant.
• a solution of gelatin and bis(vinylsulfonylmethyl)ether were overcoated at 0.9g/m 2 gelatin and 72 mg/ m 2 hardener, respectively.
• the coatings containing an ETARC coupler were prepared as follows:
• the emulsion coated layer contained 0.81 g/m 2 silver, 0.27 g/m 2 cyan dye-forming coupler, 0.16 g/m 2 ETARC coupler E-25, 4.32 g/m 2 gelatin and surfactant.
• a solution of gelatin and bis(vinylsulfonylmethyl)ether were overcoated at 0.9 g/m 2 gelatin and 72 mg/ m 2 hardener, respectively.
• Each of the film coatings were exposed for 0.01 sec to a 5500 K color temperature tungsten light source filtered through a 2B Kodak Wratten filter and a 0 to 4 density step tablet.
• the exposed film coatings were processed using the Kodak Flexicolor TM C-41 color negative film process.
• Adjusted Speed is reported in relative log speed units, where a speed difference of 1 relative log speed unit is equal to an exposure difference of 0.01 log E, where E represents exposure in lux-seconds. Speed was measured on the characteristic curve at the intersection of the extrapolated straight line portion of the characteristic curve with the straight line extrapolation of the D min segment of the characteristic curve. Adjusted speed is measured speed that has been adjusted to eliminate the differences in measured granularity. Granularity was measured using a 48 ⁇ m aperture. As is generally recognized, a speed difference of 7 grain units is equivalent to a speed difference of 1 stop (0.30 log E or 30 relative log speed units).
• Adjusted Speed is commonly used to compare the performance of emulsions that differ in both speed and granularity.
• Gamma is the slope of the straight line portion of the characteristic curve.

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• 1999
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