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
  • G03C1/06—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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
• • 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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03511—Bromide content
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03541—Cubic grains

Definitions

• This invention relates to the use of a fragmentable two electron donor with light-sensitive, nontabular silver halide emulsions having equivalent spherical diameters less than or equal to 0.35 ⁇ m..
• Fragmentable two electron donors are compounds that have been designed to undergo a bond fragmentation reaction after capturing the photohole created by absorption of light in a silver halide emulsion.
• the radical resulting from this bond fragmentation reaction is designed to be sufficiently energetic so as to inject an electron into the silver halide emulsion. Consequently, absorption of one photon by a silver halide emulsion containing a fragmentable two electron donor results in creation of two electrons in the silver halide emulsion, the first resulting from the initial absorption of the photon and the second resulting from the sequence of reactions caused by capture of the photohole at the fragmentable two electron donor. The production of this second electron leads to increased photographic speed. Fragmentable two electron donors have been described in U.S.
• These references disclose speed gains associated with the use of fragmentable two-electron donors in a wide variety of silver halide emulsions.
• addition of a fragmentable two-electron donor to an emulsion increases the fog, so that it becomes necessary to limit the amount of fragmentable two-electron donor used in order to avoid excessive fog. In such cases, the extent of practical speed gain obtainable from the fragmentable two-electron donor may be reduced.
• Small 3D emulsions i.e. nontabular emulsions with equivalent spherical diameters (ESD) ⁇ 0.35 ⁇ m
• ESD equivalent spherical diameters
• These emulsions offer low granularity owing to their small volume and high sharpness (acutance) owing to their reduced propensity to scatter light. Consequently, such emulsions are frequently used as slow components in camera-speed color negative multilayer films. They are also used to supply most of the range of emulsions, fast to slow, required for duplicating films used in photo labs and the motion picture industry. Such emulsions are also useful in microfilm.
• the small size of the emulsions limits the speed of photographic materials based on these emulsions. Higher speed at small grain size would allow shorter exposure times and/or lower intensity exposures which could be translated into improved throughput in high speed film printers or lower cost exposure sources.
• One aspect of this invention comprises a silver halide photographic element comprising at least one silver halide emulsion layer comprising 3D emulsion grains having an equivalent spherical diameter of less than or equal to 0.35 ⁇ m and said layer further comprises a fragmentable electron donor compound of the formula X-Y' or a compound which contains a moiety of the formula -X-Y'; wherein X is an electron donor moiety, Y' is a leaving proton H or a leaving group Y, with the proviso that if Y' is a proton, a base, ⁇ - , is covalently linked directly or indirectly to X, and wherein:
• This invention provides 3D emulsions of small size with enhanced photographic speed. Such emulsions are particularly useful in photographic elements where excellent image structure (i.e. low granularity and high sharpness) is required.
• 3D emulsion is one in which at least 50 percent of total grain projected area is accounted for by 3D grains.
• 3D grain refers to nontabular morphologies, for example cubes, octahedra, rods and spherical grains, and to tabular grains having an aspect ratio of less than 2.
• emulsion size has been measured by turbidimetric techniques as described in Particle Characterization , vol. 2, pages 14-19, 1985.
• the measurement yields an equivalent spherical volume/turbidity mean diameter.
• ESD equivalent spherical diameters
• Particles having morphologies other than spherical will be related to this measurement by having a volume equivalent to a sphere having a diameter equal to the ESD.
• Emulsions with ESD's less than or equal to 0.25 ⁇ m are preferred for our invention and emulsions with ESD's less than or equal to 0.15 ⁇ m are particularly preferred. High acutance and low graininess associated with these small 3D emulsions are much sought after for slow record components in camera-speed films, for all the components in a duplicating film, and in microfilms.
• the silver halide emulsions employed in the photographic elements of the present invention may be negative-working, such as surface-sensitive emulsions or unfogged internal latent image forming emulsions, or positive working emulsions of the internal latent image forming type (that are fogged during processing).
• negative-working such as surface-sensitive emulsions or unfogged internal latent image forming emulsions, or positive working emulsions of the internal latent image forming type (that are fogged during processing).
• Suitable emulsions and their preparation as well as methods of chemical and spectral sensitization are described in Research Disclosure I, Sections I through V. Color materials and development modifiers are described in Sections V through XX.
• Vehicles which can be used in the photographic elements are described in Section II, and various additives such as brighteners, antifoggants, stabilizers, light absorbing and scattering materials, hardeners, coating aids, plasticizers, lubricants and matting agents are described, for example, in Sections VI through XIII. Manufacturing methods are described in all of the sections, layer arrangements particularly in Section XI, exposure alternatives in Section XVI, and processing methods and agents in Sections XIX and XX.
• a negative image can be formed.
• a positive (or reversal) image can be formed although a negative image is typically first formed.
• the morphology of the 3D silver halide grains may be octahedral, cubic, or polymorphic. Emulsions with cubic morphology are preferred.
• the silver halide used in the photographic elements may be silver iodobromide, silver bromide, silver chloride, silver chlorobromide, silver iodochloride, silver iodobromochloride, and the like. Silver bromide or silver iodobromide emulsions are preferred and silver iodobromide emulsions are particularly preferred.
• the halides are named in their order of ascending concentrations.
• the silver halide grains to be used in the invention may be prepared according to methods known in the art, such as those described in Research Disclosure I and James, The Theory of the Photographic Process. These include methods such as ammoniacal emulsion making, neutral or acidic emulsion making, and others known in the art. These methods generally involve mixing a water soluble silver salt with a water soluble halide salt in the presence of a protective colloid, and controlling the temperature, pAg, pH values, etc, at suitable values during formation of the silver halide by precipitation.
• one or more dopants can be introduced to modify grain properties.
• any of the various conventional dopants disclosed in Research Disclosure I, Section I. Emulsion grains and their preparation, subsection G. Grain modifying conditions and adjustments, paragraphs (3), (4) and (5), can be present in the emulsions of the invention.
• a dopant capable of increasing imaging speed by forming a shallow electron trap (hereinafter also referred to as a SET) as discussed in Research Disclosure Item 36736 published November 1994.
• the SET dopants are effective at any location within the grains. Generally better results are obtained when the SET dopant is incorporated in the exterior 50 percent of the grain, based on silver. An optimum grain region for SET incorporation is that formed by silver ranging from 50 to 85 percent of total silver forming the grains.
• the SET can be introduced all at once or run into the reaction vessel over a period of time while grain precipitation is continuing. Generally SET forming dopants are contemplated to be incorporated in concentrations of at least 1 X 10 -7 mole per silver mole up to their solubility limit, typically up to about 5 X 10 -4 mole per silver mole.
• SET dopants are known to be effective to reduce reciprocity failure.
• the use of iridium hexacoordination complexes or Ir +4 complexes as SET dopants is advantageous.
• Non-SET dopants Iridium dopants that are ineffective to provide shallow electron traps
• Iridium dopants that are ineffective to provide shallow electron traps can also be incorporated into the grains of the silver halide grain emulsions to reduce reciprocity failure.
• the Ir can be present at any location within the grain structure.
• a preferred location within the grain structure for Ir dopants to produce reciprocity improvement is in the region of the grains formed after the first 60 percent and before the final 1 percent (most preferably before the final 3 percent) of total silver forming the grains has been precipitated.
• the dopant can be introduced all at once or run into the reaction vessel over a period of time while grain precipitation is continuing.
• reciprocity improving non-SET Ir dopants are contemplated to be incorporated at their lowest effective concentrations.
• the contrast of the photographic element of can be further increased by doping the grains with a hexacoordination complex containing a nitrosyl or thionitrosyl ligand (NZ dopants) as disclosed in McDugle et al U.S. Patent 4,933,272.
• the contrast increasing dopants can be incorporated in the grain structure at any convenient location. However, if the NZ dopant is present at the surface of the grain, it can reduce the sensitivity of the grains. It is therefore preferred that the NZ dopants be located in the grain so that they are separated from the grain surface by at least 1 percent (most preferably at least 3 percent) of the total silver precipitated in forming the silver iodochloride grains.
• Preferred contrast enhancing concentrations of the NZ dopants range from 1 X 10 -11 to 4 X 10 -8 mole per silver mole, with specifically preferred concentrations being in the range from 10 -10 to 10 -8 mole per silver mole.
• concentration ranges for the various SET, non-SET Ir and NZ dopants have been set out above, it is recognized that specific optimum concentration ranges within these general ranges can be identified for specific applications by routine testing. It is specifically contemplated to employ the SET, non-SET Ir and NZ dopants singly or in combination. For example, grains containing a combination of an SET dopant and a non-SET Ir dopant are specifically contemplated. Similarly SET and NZ dopants can be employed in combination. Also NZ and Ir dopants that are not SET dopants can be employed in combination. Finally, the combination of a non-SET Ir dopant with a SET dopant and an NZ dopant. For this latter three-way combination of dopants it is generally most convenient in terms of precipitation to incorporate the NZ dopant first, followed by the SET dopant, with the non-SET Ir dopant incorporated last.
• Photographic emulsions generally include a vehicle for coating the emulsion as a layer of a photographic element.
• Useful vehicles include both naturally occurring substances such as proteins, protein derivatives, cellulose derivatives (e.g., cellulose esters), gelatin (e.g., alkali-treated gelatin such as cattle bone or hide gelatin, or acid treated gelatin such as pigskin gelatin), deionized gelatin, gelatin derivatives (e.g., acetylated gelatin, phthalated gelatin, and the like), and others as described in Research Disclosure I.
• Also useful as vehicles or vehicle extenders are hydrophilic water-permeable colloids.
• the vehicle can be present in the emulsion in any amount useful in photographic emulsions.
• the emulsion can also include any of the addenda known to be useful in photographic emulsions.
• the silver halide to be used in the invention may be advantageously subjected to chemical sensitization.
• Compounds and techniques useful for chemical sensitization of silver halide are known in the art and described in Research Disclosure I and the references cited therein.
• Compounds useful as chemical sensitizers include, for example, active gelatin, sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium, phosphorous, or combinations thereof.
• Chemical sensitization is generally carried out at pAg levels of from 5 to 10, pH levels of from 4 to 8, and temperatures of from 30 to 80°C, as described in Research Disclosure I , Section IV (pages 510-511).
• the silver halide may be sensitized by sensitizing dyes by any method known in the art, such as described in Research Disclosure I .
• the dye may be added to an emulsion of the silver halide grains and a hydrophilic colloid at any time prior to (e.g., during or after chemical sensitization) or simultaneous with the coating of the emulsion on a photographic element.
• the dyes may, for example, be added as a solution in water or an alcohol.
• the dye/silver halide emulsion may be mixed with a dispersion of color image-forming coupler immediately before coating or in advance of coating (for example, 2 hours). Typical sensitizing for use with fragmentable electron donors are described in U.S. Patent No. 5,747,236.
• the silver halide emulsion contains a fragmentable electron donating (FED) compound which enhances the sensitivity of the emulsion.
• the fragmentable electron donating compound is of the formula X-Y' or a compound which contains a moiety of the formula -X-Y'; wherein X is an electron donor moiety, Y' is a leaving proton H or a leaving group Y, with the proviso that if Y' is a proton, a base, ⁇ - , is covalently linked directly or indirectly to X, and wherein:
• V oxidation potentials
• E 1 is preferably no higher than about 1.4 V and preferably less than about 1.0 V.
• the oxidation potential is preferably greater than 0, more preferably greater than about 0.3 V.
• E 1 is preferably in the range of about 0 to about 1.4 V, and more preferably from about 0.3 V to about 1.0 V.
• the oxidation potential, E 2 , of the radical X • is equal to or more negative than -0.7V, preferably more negative than about - 0.9 V.
• E 2 is preferably in the range of from about -0.7 to about -2 V, more preferably from about -0.8 to about -2 V and most preferably from about-0.9 to about -1.6 V.
• 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 •+ .
• Preferred X groups are of the general formula: or 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.
• R that is R without a subscript
• NR 2 a designation such as-OR (NR 2 ) indicates that either -OR or -NR 2 can be present.
• 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 ⁇ -
• the base is preferably the conjugate base of an acid of pKa between about 1 and about 8, preferably about 2 to about 7. Collections of pKa values are available (see, for example: Dissociation Constants of Organic Bases in Aqueous Solution, D. D. Perrin (Butterworths, London, 1965); CRC Handbook of Chemistry and Physics, 77th ed, D. R. Lide (CRC Press, Boca Raton, Fl, 1996)). Examples of useful bases are included in Table I.
• the base, ⁇ - is a carboxylate, sulfate or amine oxide.
• the fragmentable electron donating compound 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 compounds 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'
• Z is a light absorbing group including, for example, cyanine dyes, complex cyanine dyes, merocyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, styryl dyes, oxonol dyes, hemioxonol dyes, and hemicyanine dyes.
• 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: -CH 2 CH 2 SH and
• 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 about 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 compounds include:
• the fragmentable electron donors of the present invention can be included in a silver halide emulsion by direct dispersion in the emulsion, or they may be dissolved in a solvent such as water, methanol or ethanol for example, or in a mixture of such solvents, and the resulting solution can be added to the emulsion.
• the compounds of the present invention may also be added from solutions containing a base and/or surfactants, or may be incorporated into aqueous slurries or gelatin dispersions and then added to the emulsion.
• the fragmentable electron donor may be used as the sole sensitizer in the emulsion. However, in preferred embodiments of the invention a sensitizing dye is also added to the emulsion.
• the compounds can be added before, during or after the addition of the sensitizing dye.
• the amount of electron donor which is employed in this invention may range from as little as 1 x 10 -8 mole per mole of silver in the emulsion to as much as about 0.1 mole per mole of silver, preferably from about 5 x 10 -7 to about 0.05 mole per mole of silver.
• the oxidation potential E 1 for the XY moiety of the electron donating sensitizer is a relatively low potential, it is more active, and relatively less agent need be employed.
• the oxidation potential for the XY moiety of the electron donating sensitizer is relatively high, a larger amount thereof, per mole of silver, is employed.
• the fragmentable electron donating sensitizer is more closely associated with the silver halide grain and relatively less agent need be employed.
• fragmentable one-electron donors relatively larger amounts per mole of silver are also employed.
• the electron donor can also be incorporated into the emulsion after exposure by way of a pre-developer bath or by way of the developer bath itself.
• Fragmentable electron donating compounds are described more fully in U.S. Patents 5,747,235, 5,747,236, 5,994,051, and 6,010,841, and published European Patent Applications 893,731 and 893,732.
• Typical antifoggants are discussed in Section VI of Research Disclosure I, for example tetraazaindenes, mercaptotetrazoles, polyhydroxybenzenes, hydroxyaminobenzenes, combinations of a thiosulfonate and a sulfinate, and the like.
• hydroxybenzene compounds polyhydroxybenzene and hydroxyaminobenzene compounds
• hydroxybenzene compounds are preferred as they are effective for lowering fog without decreasing the emulsion sensitvity.
• hydroxybenzene compounds are:
• V and V' each independently represent -H, -OH, a halogen atom, -OM (M is alkali metal ion), an alkyl group, a phenyl group, an amino group, a carbonyl group, a sulfone group, a sulfonated phenyl group, a sulfonated alkyl group, a sulfonated amino group, a carboxyphenyl group, a carboxyalkyl group, a carboxyamino group, a hydroxyphenyl group, a hydroxyalkyl group, an alkylether group, an alkylphenyl group, an alkylthioether group, or a phenylthioether group.
• M is alkali metal ion
• Hydroxybenzene compounds may be added to the emulsion layers or any other layers constituting the photographic material of the present invention.
• the preferred amount added is from 1 x 10 -3 to 1 x 10 -1 mol, and more preferred is 1 x 10 -3 to 2 x 10 -2 mol, per mol of silver halide.
• the emulsion layer of the photographic element of the invention can comprise any one or more of the light sensitive layers of the photographic element.
• the photographic elements made in accordance with the present invention can be black and white elements, single color elements or multicolor elements.
• Multicolor elements contain dye image-forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum.
• the layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art.
• the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer.
• a typical multicolor photographic element comprises a support bearing a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler.
• the element can contain additional layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like. All of these can be coated on a support which can be transparent or reflective (for example, a paper support).
• Photographic elements of the present invention may also usefully include a magnetic recording material as described in Research Disclosure, Item 34390, November 1992, or a transparent magnetic recording layer such as a layer containing magnetic particles on the underside of a transparent support as in US 4,279,945 and US 4,302,523.
• the element typically will have a total thickness (excluding the support) of from 5 to 30 microns. While the order of the color sensitive layers can be varied, they will normally be red-sensitive, green-sensitive and blue-sensitive, in that order on a transparent support, (that is, blue sensitive furthest from the support) and the reverse order on a reflective support being typical.
• the present invention also contemplates the use of photographic elements of the present invention in what are often referred to as single use cameras (or "film with lens” units). These cameras are sold with film preloaded in them and the entire camera is returned to a processor with the exposed film remaining inside the camera. Such cameras may have glass or plastic lenses through which the photographic element is exposed.
• the photographic elements of the present invention may also use colored couplers (e.g. to adjust levels of interlayer correction) and masking couplers such as those described in EP 213 490; Japanese Published Application 58-172,647; U.S. Patent 2,983,608; German Application DE 2,706,117C; U.K. Patent 1,530,272; Japanese Application A-113935; U.S. Patent 4,070,191 and German Application DE 2,643,965.
• the masking couplers may be shifted or blocked.
• the photographic elements may also contain materials that accelerate or otherwise modify the processing steps of bleaching or fixing to improve the quality of the image.
• Bleach accelerators described in EP 193 389; EP 301 477; U.S. 4,163,669; U.S. 4,865,956; and U.S. 4,923,784 are particularly useful.
• nucleating agents, development accelerators or their precursors UK Patent 2,097,140; U.K. Patent 2,131,188
• development inhibitors and their precursors U.S. Patent No. 5,460,932; U.S. Patent No. 5,478,711
• electron transfer agents U.S. 4,859,578; U.S.
• antifogging and anti color-mixing agents such as derivatives of hydroquinones, aminophenols, amines, gallic acid; catechol; ascorbic acid; hydrazides; sulfonamidophenols; and non color-forming couplers.
• the elements may also contain filter dye layers comprising colloidal silver sol or yellow and/or magenta filter dyes and/or antihalation dyes (particularly in an undercoat beneath all light sensitive layers or in the side of the support opposite that on which all light sensitive layers are located) either as oil-in-water dispersions, latex dispersions or as solid particle dispersions. Additionally, they may be used with "smearing" couplers (e.g. as described in U.S. 4,366,237; EP 096 570; U.S. 4,420,556; and U.S. 4,543,323.) Also, the couplers may be blocked or coated in protected form as described, for example, in Japanese Application 61/258,249 or U.S. 5,019,492.
• the photographic elements may further contain other image-modifying compounds such as "Development Inhibitor-Releasing” compounds (DIR's).
• DIR's Development Inhibitor-Releasing compounds
• DIR compounds are also disclosed in "Developer-Inhibitor-Releasing (DIR) Couplers for Color Photography," C.R. Barr, J.R. Thirtle and P.W. Vittum in Photographic Science and Engineering, Vol. 13, p. 174 (1969).
• the concepts of the present invention may be employed to obtain reflection color prints as described in Research Disclosure , November 1979, Item 18716.
• the emulsions and materials to form elements of the present invention may be coated on pH adjusted support as described in U.S. 4,917,994; with epoxy solvents (EP 0 164 961); with additional stabilizers (as described, for example, in U.S. 4,346,165; U.S. 4,540,653 and U.S. 4,906,559); with ballasted chelating agents such as those in U.S. 4,994,359 to reduce sensitivity to polyvalent cations such as calcium; and with stain reducing compounds such as described in U.S. 5,068,171 and U.S.
• Photographic elements of the present invention are preferably imagewise exposed using any of the known techniques, including those described in Research Disclosure I , section XVI. This typically involves exposure to light in the visible region of the spectrum, and typically such exposure is of a live image through a lens, although exposure can also be exposure to a stored image (such as a computer stored image) by means of light emitting devices (such as light emitting diodes, CRT and the like). Where photographic elements of the present invention are intended as duplicating films or as print materials, the exposure is typically made by passing light in the visible region through a color negative or positive image and appropriate focussing lenses.
• Photographic elements comprising the composition of the invention can be processed in any of a number of well-known photographic processes utilizing any of a number of well-known processing compositions, described, for example, in Research Disclosure I , or in T.H. James, editor, The Theory of the Photographic Process , 4th Edition, Macmillan, New York, 1977.
• a negative working element the element is treated with a color developer (that is one which will form the colored image dyes with the color couplers), and then with a oxidizer and a solvent to remove silver and silver halide.
• the element is first treated with a black and white developer (that is, a developer which does not form colored dyes with the coupler compounds) followed by a treatment to fog silver halide (usually chemical fogging or light fogging), followed by treatment with a color developer.
• a black and white developer that is, a developer which does not form colored dyes with the coupler compounds
• a treatment to fog silver halide usually chemical fogging or light fogging
• a color developer usually chemical fogging or light fogging
• 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 Bissonette U.S. Patents 3,748,138, 3,826,652, 3,862,842 and 3,989,526 and Travis U.S. Patent 3,765,891, and/or a peroxide oxidizing agent as illustrated by Matejec U.S. Patent 3,674,490, Research Disclosure, Vol. 116, December, 1973, Item 11660, and Bissonette 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 Dunn et al U.S.
• Patent 3,822,129, Bissonette U.S. Patents 3,834,907 and 3,902,905 Bissonette et al U.S. Patent 3,847,619, Mowrey U.S. Patent 3,904,413, Hirai et al U.S. Patent 4,880,725, Iwano U.S. Patent 4,954,425, Marsden et al U.S. Patent 4,983,504, Evans et al U.S. Patent 5,246,822, Twist U.S. Patent No.
• a silver iodobromide cubic emulsion (Emulsion E-1) was prepared containing 3.5 % total iodide distributed as a homogeneous run iodide phase. The following solutions were made:
• Solution A was placed in a 20 liter reaction vessel and heated to 44 degrees C.
• Solutions B and C were added in a double jet fashion at a constant rate while the pAg for the solution was held at 9.00 by adjusting the flow of solution C.
• solution D was added for a period of one minute.
• Solution D addition stopped, the flow of solution C was controlled such that pAg was reduced to 7.65 over a period of three minutes.
• addition was stopped and the solution was cooled to 40 degrees and subjected to ultrafiltration.
• the monodispersed cubic emulsion grains had an average ESD of 0.15 ⁇ m as determined by discrete wavelength turbidimetry.
• a silver iodobromide cubic emulsion (Emulsion E-2) was prepared containing 3.4 % total iodide distributed as a homogeneous run iodide phase. The following solutions were made:
• Solution A was placed in a 20 liter reaction vessel and heated to 50 degrees C. 34 ml of solutions B and C were added in a double jet fashion at an equal and constant rate for 30 seconds. During the next three minutes the addition rate for solution B was held at 42.6 ml/min and the flow of solution C was controlled such that pAg was raised to 7.73. After achieving pAg of 7.73 the flow rate for solution B was reduced to 21.3 ml/min and then ramped to a rate of 23 ml/min over a two minute period, during which Solution D was added at a constant rate, and solution C flow rates were adjusted to control pAg at 7.73.
• the flow rate for solution B was set to 45.9 ml/min and, over the next 33.1 minutes, linearly ramped to 155.5 ml/min, while solution C flow rates were controlled to maintain a constant pAg at 7.73. After this, addition was stopped and the solution was cooled to 40 degrees and subjected to ultrafiltration.
• the monodispersed cubic emulsion grains had an average ESD of 0.33 ⁇ m as determined by discrete wavelength turbidimetry.
• Emulsion E-3 was made in a manner identical to E-2 except that solution A was changed to the following: A: 9.1 liters water, 202.8 g of bone gelatin, 4.79 grams of NaBr, 2.25 grams of PLURONIC 31R1®, 2.13 g of thioether (Ethanol, 2,2'-(1,2-ethanediylbis(thio))bis-)
• the monodispersed cubic emulsion grains thus made had an average ESD of 0.40 ⁇ m as determined by discrete wavelength turbidimetry.
• Emulsions E-1, E-2 and E-3 were chemically and spectrally sensitized using:
• the antifoggant and metal sequestrant, HB-3 was added prior to coating.
• the two electron donating sensitizing agent FED-2 was also added before coating.
• Coatings were then prepared consisting of the green-sensitized silver halide emulsion at a laydown of 75 mg/ft 2 (0.825 g/m 2 ), 150 mg/ft 2 (1.65 g/m 2 ) of the cyan dye forming coupler C1, and a gelatin vehicle at 300 mg/ft 2 (3.3 g/m 2 ).
• An overcoat of gelatin at 250 mg/ft 2 (2.75 g/m 2 ) was subsequently applied containing bisvinylsulfonylmethyl ether hardener 1.8% wt/wt of gelatin.
• each of the coating strips was exposed for 0.01 sec to a 3000 K color temperature tungsten lamp filtered to give an effective color temperature of 5500K and further filtered a Kodak Wratten filter number 9 and a step wedge ranging in density from 0 to 4 density units in 0.2 density steps.
• the exposed film strips were processed in standard C-41 chemistry. Speed was metered at the point 0.15 density units above dmin and is reported in units of log relative sensitivity (log S).
• Table I summarizes the data for the green sensitized emulsions.
• emulsion E-1 it can be seen that even the highest level of FED-2, which yielded a speed increase of 0.11 log S, gave a corresponding dmin increase of only 0.014.
• Emulsion E-2 the lowest level of FED-2 gave a similar speed increase of 0.10 log S with a moderate (but acceptable) dmin increase of 0.047.
• the lowest level of FED-2 gave a similar speed increase (0.13 log S) but with an unacceptable a dmin increase of 0.094 density units.
• a silver iodobromide cubic emulsion (Emulsion E-4) was prepared containing 3.3 % total iodide distributed as a homogeneous run iodide phase. The following solutions were made:
• Solution A was placed in a 20 liter reaction vessel and heated to 46 degrees C.
• Solutions B and C were added in a double jet fashion at a constant rate while the pAg for the solution was held at 8.94 by adjusting the flow of solution C.
• solution D was added for a period of one minute.
• Solution D addition stopped, the flow of solution C was controlled such that pAg was reduced to 7.60 over a period of three minutes.
• addition was stopped and the solution was cooled to 40 degrees and subjected to ultrafiltration.
• the monodispersed cubic emulsion grains had an average ESD of 0.17 ⁇ m as determined by discrete wavelength turbidimetry.
• a silver iodobromide cubic emulsion (Emulsion E-5) was prepared containing 3.3 % total iodide distributed as a homogeneous run iodide phase. The following solutions were made:
• Solution A was placed in a 20 liter reaction vessel and heated to 60 degrees C.
• Solutions B and C were added in a double jet fashion at a constant rate while the pAg for the solution was held at 8.55 by adjusting the flow of solution C.
• solution D was added for a period of one minute.
• Solution D addition stopped, the flow of solution C was controlled such that pAg was reduced to 7.26 over a period of three minutes.
• addition was stopped and the solution was cooled to 40 degrees and subjected to ultrafiltration.
• the monodispersed cubic emulsion grains had an average ESD of 0.20 ⁇ m as determined by discrete wavelength turbidimetry.
• a silver iodobromide cubic emulsion (Emulsion E-4) was prepared containing 3.3 % total iodide distributed as a homogeneous run iodide phase. The following solutions were made:
• Solution A was placed in a 20 liter reaction vessel and heated to 79 degrees C.
• Solutions B and C were added in a double jet fashion at a constant rate while the pAg for the solution was held at 8.08 by adjusting the flow of solution C.
• solution D was added for a period of one minute.
• Solution D addition stopped, the flow of solution C was controlled such that pAg was reduced to 6.86 over a period of three minutes.
• addition was stopped and the solution was cooled to 40 degrees and subjected to ultrafiltration.
• the monodispersed cubic emulsion grains had an average ESD of 0.27 ⁇ m as determined by discrete wavelength turbidimetry.
• Emulsions E-4, E-5 and E-6 were chemically and spectrally sensitized using:
• the antifoggant and metal sequestrant, HB-3 was added prior to coating.
• the two electron donating sensitizing agent FED-2 was also added before coating.
• Coatings were then prepared consisting of sensitized silver halide emulsion at a laydown of 75 mg/ft 2 (0.825 g/m 2 ), 150 mg/ft 2 (1.65 g/m 2 ) of the cyan dye forming coupler C1, and a gelatin vehicle at 300 mg/ft 2 (3.3 g/m 2 ).
• An overcoat of gelatin at 250 mg/ft 2 (2.75 g/m 2 ) was subsequently applied containing bisvinylsulfonylmethyl ether hardener 1.8% wt/wt of gelatin.
• samples from each of the coatings was exposed for 0.01 sec to a 3000 K color temperature tungsten lamp filtered to give an effective color temperature of 5500K and further filtered a Kodak Wratten filter number 2B and a step wedge ranging in density from 0 to 4 density units in 0.2 density steps.
• the exposed film strips were processed in standard C-41 chemistry.
• Speed was metered at the point 0.15 density units above the minimum density and reported in units of log relative sensitivity (log S).
• Table II summarizes the data for the blue sensitized emulsions.
• E-4 For the smallest emulsion, E-4, it can be seen that even the highest level of FED-2 (48 mg/Ag-mole), which yielded a speed increase of 0.24 log S, gave a corresponding dmin increase of only 0.06 density units.
• emulsion E-5 For the same dmin increase, emulsion E-5, with an ESD of 0.20 ⁇ m, gave a speed increase of 0.18 log S when treated with 24 mg/mole Ag of FED-2.
• the largest emulsion, treated with a substantially lower level of FED-2 (6mg/Ag-mole) gave a small speed increase (0.04 log S) and a dmin increase of 0.12 density units.
• a silver iodobromide cubic emulsion (Emulsion E-7) was prepared containing 3.3 % total iodide distributed as a homogeneous run iodide phase. The following solutions were made:
• Solution A was placed in a 20 liter reaction vessel and brought to 36 degrees C.
• Solutions B and C were added in a double jet fashion at a constant rate while the pAg for the solution was held at 9.23 by adjusting the flow of solution C.
• solution D was added for a period of one minute.
• Solution D addition stopped, the flow of solution C was controlled such that pAg was reduced to 7.85 over a period of three minutes.
• addition was stopped and the solution was warmed to 40 degrees and subjected to ultrafiltration.
• the monodispersed cubic emulsion grains had an average ESD of 0.07 ⁇ m as determined by discrete wavelength turbidimetry.
• a silver iodobromide cubic emulsion (Emulsion E-8) was prepared containing 3.3 % total iodide distributed as a homogeneous run iodide phase. The following solutions were made:
• Solution A was placed in a 20 liter reaction vessel and heated to 41.5 degrees C.
• Solutions B and C were added in a double jet fashion at a constant rate while the pAg for the solution was held at 9.06 by adjusting the flow of solution C.
• solution D was added for a period of one minute.
• Solution D addition stopped, the flow of solution C was controlled such that pAg was reduced to 7.70 over a period of three minutes.
• addition was stopped and the solution was cooled to 40 degrees and subjected to ultrafiltration.
• the monodispersed cubic emulsion grains had an average ESD of 0.11 ⁇ m as determined by discrete wavelength turbidimetry.
• a silver iodobromide cubic emulsion (Emulsion E-9) was prepared containing 3.3 % total iodide distributed as a homogeneous run iodide phase. The following solutions were made:
• Solution A was placed in a 20 liter reaction vessel and heated to 40 degrees C.
• Solutions B and C were added in a double jet fashion at a constant rate while the pAg for the solution was held at 9.11 by adjusting the flow of solution C.
• solution D was added for a period of one minute.
• Solution D addition stopped, the flow of solution C was controlled such that pAg was reduced to 7.74 over a period of three minutes.
• addition was stopped, the solution was maintained at 40 degrees and subjected to ultrafiltration.
• the monodispersed cubic emulsion grains had an average ESD of 0.13 ⁇ m as determined by discrete wavelength turbidimetry.
• a silver iodobromide cubic emulsion (Emulsion E-10) was prepared containing 3.3 % total iodide distributed as a homogeneous run iodide phase. The following solutions were made:
• Solution A was placed in a 20 liter reaction vessel and heated to 51.5 degrees C. Solutions B and C were added in a double jet fashion at a constant rate while the pAg for the solution was held at 8.77 by adjusting the flow of solution C. After one minute, solution D was added for a period of one minute. One minute after Solution D addition stopped, the flow of solution C was controlled such that pAg was reduced to 7.44 over a period of three minutes. After another 24.1 minutes, addition was stopped, the solution was cooled to 40 degrees and subjected to ultrafiltration.
• the monodispersed cubic emulsion grains had an average ESD of 0.18 ⁇ m as determined by discrete wavelength turbidimetry.
• Emulsions E-7 through E-10 were chemically and spectrally sensitized using:
• Coatings were then prepared consisting of sensitized silver halide emulsion at a laydown of 40 mg/ft 2 (0.44 g/m 2 ), 60 mg/ft 2 (0.66 g/m 2 ) of the cyan dye forming coupler C1, and a gelatin vehicle at 300 mg/ft 2 (3.3 g.m 2 ).
• An overcoat of gelatin at 50 mg/ft 2 (0.55 g/m 2 ) was subsequently applied containing bisvinylsulfonylmethane hardener 1.4% wt/wt of gelatin.
• samples from each of the coatings was exposed for 0.01 sec to a 3000 K color temperature tungsten lamp filtered to give an effective color temperature of 5500K and further filtered a Kodak Wratten filter number 2B and a step wedge ranging in density from 0 to 4 density units in 0.2 density steps.
• the exposed film strips were processed in standard C-41 chemistry.
• Speed was metered at the point 0.15 density units above the minimum density and reported in units of log relative sensitivity (log S).
• Table III summarizes the data for the red sensitized emulsions.
• E-7 For the smallest emulsion, E-7, it can be seen that even the highest level of FED-2 (25 mg/Ag-mole), which yielded a speed increase of 0.33 log S, gave no significant dmin increase.
• Emulsion E-8 with an ESD of 0.11 ⁇ m, gave a speed increase of 0.10 log S when treated with 2 mg/mole Ag of FED-2. Interpolating, one would expect that a speed increase of about 0.20 log S could be achieved with a dmin increase of about 0.05.
• Emulsion E-9 with an ESD of 0.13 ⁇ m, gave results similar to E-8 but at about half the FED-2 level.
• Emulsion E-11
• a silver iodobromide cubic emulsion (Emulsion E-11) was prepared exactly like emulsion E-7 as the check for making variations in the amounts of K 2 IrCl 6 used in the precipitations and N-2-propynyl-2-benzoxazolamine used in the sensitizations.
• Emulsion E-12 is a first Emulsion E-12.
• This emulsion was identical to emulsion E-11 except that no N-2-propynyl-2-benzoxazolamine was used in the sensitization step.
• Emulsion E-13 is a diagrammatic representation of Emulsion E-13:
• a silver iodobromide cubic emulsion (Emulsion E-13 ) was prepared exactly like emulsion E-11 except that Solution D had the following composition: D: 19.2 mg K 2 IrCl 6 dissolved in 46.5 ml of water - i.e., twice the amount in emulsion E-11.
• Emulsion E-14 is a first Emulsion E-14:
• This emulsion was identical to emulsion E-13 except that no N-2-propynyl-2-benzoxazolamine was used in the sensitization step.
• Emulsion E-15 is a diagrammatic representation of Emulsion E-15.
• a silver iodobromide cubic emulsion (Emulsion E-15 ) was prepared exactly like emulsions E-11 and E-13 except that Solution D was omitted - i.e., emulsion E-15 contained no K 2 IrCl 6 .
• Emulsion E-16 is a diagrammatic representation of Emulsion E-16.
• This emulsion was identical to emulsion E-15 except that no N-2-propynyl-2-benzoxazolamine was used in the sensitization step.
• Emulsions E-11 through E-16 were coated and evaluated like emulsions E-7 through E-10.
• Table IV shows, first, that there was a relatively small effect due to variations in the amount of K 2 IrCl 6 used in the precipitations. Indeed, there was a small speed loss associated with increasing amounts of K 2 IrCl 6 . The slightly greater effect of FED-2 with higher levels of K 2 IrCl 6 almost exactly compensated for the speed loss associated with the K 2 IrCl 6 such that emulsions E-11, E-13 and E-15 all had the same speed with FED-2, within experimental uncertainty.
• Table IV also shows that, although omission of N-2-propynyl-2-benzoxazolamine from the sensitization caused some speed loss, in these cases the speed gain realized from the use of FED-2 in coating was substantially greater and, in fact, largely offset the loss from the change in sensitization procedure.
• Table IV illustrates that the advantageous effect of FED-2 in this small cubic emulsion can be seen in both the presence and absence of Ir dopant as well as in the presence or absence of the N-2-propynyl-2-benzoxazolamine.

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