EP0641459B1 - Ein farbbild erzeugende photographische elemente - Google Patents

Ein farbbild erzeugende photographische elemente Download PDF

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Publication number
EP0641459B1
EP0641459B1 EP93907625A EP93907625A EP0641459B1 EP 0641459 B1 EP0641459 B1 EP 0641459B1 EP 93907625 A EP93907625 A EP 93907625A EP 93907625 A EP93907625 A EP 93907625A EP 0641459 B1 EP0641459 B1 EP 0641459B1
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Prior art keywords
emulsion
layer
sensitized
tabular
grain
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English (en)
French (fr)
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EP0641459A1 (de
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Richard Peter Szajewski
Gary Lawrence House
Thomas Brownell Brust
Joe Edward Maskasky
Debra Lynn Hartsell
Donald Lee Black
James Parker Merrill
Anne Elizabeth Bohan
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Eastman Kodak Co
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • G03C1/0053—Tabular grain emulsions with high content of silver chloride
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—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
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/16—Methine and polymethine dyes with an odd number of CH groups with one CH group
    • 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
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • 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
    • G03C1/22—Methine and polymethine dyes with an even number of CH groups
    • 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
    • G03C2001/0055—Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
    • 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
    • G03C2001/03558—Iodide 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
    • G03C2001/03594—Size of the grains
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00—Details
    • G03C2200/01—100 crystal face
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00—Details
    • G03C2200/11—Blue-sensitive layer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00—Details
    • G03C2200/53—Red-sensitive layer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • 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
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group

Definitions

  • the invention relates to color photographic elements comprising radiation sensitive tabular grain silver halide emulsion layers.
  • Bogg U.S. Patent 4,063,951 reported the first tabular grain emulsions in which the tabular grains had parallel ⁇ 100 ⁇ major crystal faces.
  • the tabular grains of Bogg exhibited square or rectangular major faces, thus lacking the threefold symmetry of conventional tabular grain ⁇ 111 ⁇ major crystal faces.
  • Bogg employed an ammoniacal ripening process for preparing silver bromoiodide tabular grains having aspect ratios ranging from 4:1 to 1:1.
  • the average aspect ratio of the emulsion was reported to be 2, with the highest aspect ratio grain (grain A in Figure 3) being only 4.
  • Bogg states that the emulsions can contain no more than 1 percent iodide and demonstrates only a 99.5% bromide 0.5% iodide emulsion. Attempts to prepare tabular grain emulsions by the procedures of Bogg have been unsuccessful.
  • Mignot U.S. Patent 4,386,156 represents an improvement over Bogg in that the disadvantages of ammoniacal ripening were avoided in preparing a silver bromide emulsion containing tabular grains with square and rectangular major faces.
  • Mignot specifically requires ripening in the absence of silver halide ripening agents other than bromide ion (e.g., thiocyanate, thioether or ammonia).
  • DIR compounds can release development inhibitors during photographic processing and such inhibitors can be used to provide a variety of photographic effects such as decreasing gamma which can be used to control curve shape.
  • Development Inhibitor Releasing compounds have limited utility with cubic silver halide emulsions having high chloride contents because such compounds tend to have little impact on latitude or gamma when they are used with such emulsions.
  • DIR compounds often cause speed losses with such emulsions.
  • Figure 1 is a shadowed photomicrograph of carbon grain replicas of a representative emulsion of the invention, described in detail in Example 1 below. It is immediately apparent that most of the grains have orthogonal tetragonal (square or rectangular) faces. The orthogonal tetragonal shape of the grain faces indicates that they are ⁇ 100 ⁇ crystal faces.
  • tabular grains account for more than 50 percent of total grain projected area. From the definition of a tabular grain above, it is apparent that the average aspect ratio of the tabular grains can only approach 2 a minimum limit. In fact, tabular grain emulsions of the invention typically exhibit average aspect ratios of 5 or more, with high average aspect ratios (>8) being preferred. That is, preferred emulsions according to the invention are high aspect ratio tabular grain emulsions. In specifically preferred emulsions according to the invention average aspect ratios of the tabular grain population are at least 12 and optimally at least 20. Typically the average aspect ratio of the tabular grain population ranges up to 50, but higher aspect ratios of 100, 200 or more can be realized.
  • the tabular grain population accounting for at least 50 percent of total grain projected area is provided by tabular grains also exhibiting 0.2 mm.
  • the emulsions are in this instance thin tabular grain emulsions.
  • the tabular grain population can exhibit an average ECD of any photographically useful magnitude.
  • ECD's for photographic utility average ECD's of less than 10 mm are contemplated, although average ECD's in most photographic applications rarely exceed 6 mm.
  • ECD's for photographic utility average ECD's of less than 10 mm are contemplated, although average ECD's in most photographic applications rarely exceed 6 mm.
  • ultrathin tabular grain emulsions satisfying the requirements of the invention it is possible to provide intermediate aspect ratios with ECD's of the tabular grain population of 0.10 mm and less.
  • emulsions with selected tabular grain populations having higher ECD's are advantageous for achieving relatively high levels of photographic sensitivity while selected tabular grain populations with lower ECD's are advantageous in achieving low levels of granularity.
  • cubic grain nuclei being formed having one or more screw dislocations in one or more of the cubic crystal faces.
  • the cubic crystal faces that contain at least one screw dislocation thereafter accept silver halide at an accelerated rate as compared to the regular cubic crystal faces (i.e., those lacking a screw dislocation).
  • the regular cubic crystal faces i.e., those lacking a screw dislocation.
  • the grain nucleation step is initiated when a silver jet is opened to introduce silver ion into the dispersing medium.
  • Iodide ion is preferably introduced into the dispersing medium concurrently with or, optimally, before opening the silver jet.
  • Effective tabular grain formation can occur over a wide range of iodide ion concentrations ranging up to the saturation limit of iodide in silver chloride.
  • the saturation limit of iodide in silver chloride is reported by H. Hirsch, "Photographic Emulsion Grains with Cores: Part I. Evidence for the Presence of Cores", J. of Photog. Science, Vol. 10 (1962), pp. 129-134, to be 13 mole percent.
  • silver iodochloride grain nuclei are formed during the nucleation step. Minor amounts of bromide ion can be present in the dispersing medium during nucleation. Any amount of bromide ion can be present in the dispersing medium during nucleation that is compatible with at least 50 mole percent of the halide in the grain nuclei being chloride ions.
  • the grain nuclei preferably contain at least 70 mole percent and optimally at least 90 mole percent chloride ion, based on silver.
  • grain growth to obtain the emulsions of the invention can proceed according to any convenient conventional precipitation technique for the precipitation of silver halide grains bounded by ⁇ 100 ⁇ grain faces.
  • any halide or combination of halides known to form a cubic crystal lattice structure can be employed during the growth step.
  • peptizers that exhibit reduced adhesion to grain surfaces.
  • low methionine gelatin of the type disclosed by Maskasky II is less tightly absorbed to grain surfaces than gelatin containing higher levels of methionine.
  • Further moderated levels of grain adsorption can be achieved with so-called “synthetic peptizers"--that is, peptizers formed from synthetic polymers.
  • the maximum quantity of peptizer compatible with limited coalescence of grain nuclei is, of course, related to the strength of adsorption to the grain surfaces.
  • the emulsions of the invention include silver chloride, silver iodochloride emulsions, silver iodo-bromochloride emulsions and silver iodochlorobromide emulsions. Dopants, in concentrations of up to 10 -2 mole per silver mole and typically less than 10 -4 mole per silver mole, can be present in the grains.
  • Coordination ligands such as halo, aquo, cyano cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl ligands are contemplated and can be relied upon to modify photographic properties.
  • the restraining agent can satisfy the following formula: where Z represents the atoms necessary to complete a five or six membered aromatic ring structure, preferably formed by carbon and nitrogen ring atoms.
  • Preferred aromatic rings are those that contain one, two or three nitrogen atoms.
  • ring structures inciude 2H-pyrrole, pyrrole, imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, 1,3,5-triazole, pyridine, pyrazine, pyrimidine, and pyridazine.
  • Selection of preferred restraining agents and their useful concentrations can be accomplished by the following selection procedure:
  • the compound being considered for use as a restraining agent is added to a silver chloride emulsion consisting essentially of cubic grains with a mean grain edge length of 0.3 m.
  • the emulsion is 0.2 M in sodium acetate, has a pCl of 2.1, and has a pH that is at least one unit greater than the pKa of the compound being considered.
  • the emulsion is held at 75°C with the restraining agent present for 24 hours.
  • the emulsions used in this invention can be chemically sensitized with active gelatin as illustrated by T. H. James, The Theory of the Photographic Process, 4th Ed., Macmillan, 1977, pp. 67-76, or with sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium or phosphorus sensitizers or combinations of these sensitizers, such as at pAg levels of from 5 to 10, pH levels of from 5 to 8 and temperatures of from 30 to 80°C, as illustrated by Research Disclosure, Vol. 120, April, 1974, Item 12008, Research Disclosure, Vol. 134, June, 1975, Item 13452, Sheppard et al U.S.
  • One or more spectral sensitizing dyes may be employed. Dyes with sensitizing maxima at wavelengths throughout the visible and infrared spectrum and with a great variety of spectral sensitivity curve shapes are known. The choice and relative proportions of dyes depends upon the region of the spectrum to which sensitivity is desired and upon the shape of the spectral sensitivity curve desired. Dyes with overlapping spectral sensitivity curves will often yield in combination a curve in which the sensitivity at each wavelength in the area of overlap is approximately equal to the sum of the sensitivities of the individual dyes. Thus, it is possible to use combinations of dyes with different maxima to achieve a spectral sensitivity curve with a maximum intermediate to the sensitizing maxima of the individual dyes.
  • Postprocessing dye stain can be reduced by the proximity to the dyed emulsion layer of fine high-iodide grains as described by Dickerson.
  • the spectral-sensitizing dyes can be added to the emulsion as solutions in water or such solvents as methanol, ethanol, acetone or pyridine; dissolved in surfactant solutions as described by Sakai et al U.S. Patent 3,822,135; or as dispersions as described by Owens et al U.S. Patent 3,469,987 and Japanese published Patent Application (Kokai) 24185/71.
  • the dyes can be selectively adsorbed to particular crystallographic faces of the emulsion grain as a means of restricting chemical sensitization centers to other faces, as described by Mifune et al published European Patent Application 302,528.
  • the spectral sensitizing dyes may be used in conjunction with poorly adsorbed luminescent dyes, as described by Miyasaka et al published European Patent Applications 270,079, 270,082 and 278,510.
  • Instability which increases minimum density in negative-type emulsion coatings can be protected against by incorporation of stabilizers, antifoggants, antikinking agents, latent-image stabilizers and similar addenda in the emulsion and contiguous layers prior to coating.
  • Most of the antifoggants effective in the emulsions used in this invention can also be used in developers and can be classified under a few general headings, as illustrated by C.E.K. Mees, The Theory of the Photographic Process, 2Nd Ed., Macmillan, 1954, pp. 677-680.
  • latent-image stabilizers can be incorporated, such as amino acids, as illustrated by Ezekiel U.K. Patents 1,335,923, 1,378,354, 1,387,654 and 1,391,672, Ezekiel et al U.K. Patent 1,394,371, Jefferson U.S. Patent 3,843,372, Jefferson et al U.K. Patent 1,412,294 and Thurston U.K. Patent 1,343,904; carbonyl-bisulfite addition products in combination with hydroxybenzene or aromatic amine developing agents as illustrated by Seiter et al U.S.
  • Patent 3,424,583 cycloalkyl-1,3-diones as illustrated by Beckett et al U.S. Patent 3,447,926; enzymes of the catalase type as illustrated by Matejec et al U.S. Patent 3,600,182; halogen-substituted hardeners in combination with certain cyanine dyes as illustrated by Kumai et al U.S. Patent 3,881,933; hydrazides as illustrated by Honig et al U.S. Patent 3,386,831; alkenyl benzothiazolium salts as illustrated by Arai et al U.S.
  • Preferred dye image-forming compounds are coupler compounds, which react with oxidized color developing agents to form colored products, or dyes.
  • a coupler compound contains a coupler moiety COUP, which is combined with the oxidized developer species in the coupling reaction to form the dye structure.
  • a coupler compound can additionally contain a group, called a coupling-off group, that is attached to the coupler moiety by a bond that is cleaved upon reaction of the coupler compound with oxidized color developing agent.
  • Coupling-off groups can be halogen, such as chloro, bromo, fluoro, and iodo, or organic radicals that are attached to the coupler moieties by atoms such as oxygen, sulfur, nitrogen, phosphorus, and the like.
  • TIME can be any organic group which will serve to connect CAR to the PUG moiety and which, after cleavage from CAR, will in turn be cleaved from the PUG moiety.
  • This cleavage is preferably by an intramolecular nucleophilic displacement reaction of the type described in, for example, U.S. Patent No. 4,248,962, or by electron transfer along a conjugated chain as described in, for example, U.S. Patent No. 4,409,323.
  • Timing groups are represented by the structure: wherein:
  • thermodynamics should be such and the groups be so selected that an overall free energy decrease results upon ring closure, forming the bond between the nucleophilic group and the electrophilic group, and breaking the bond between the electrophilic group and the PUG.
  • nucleophilic group, linking group, and electrophilic group will yield a thermodynamic relationship favorable to breaking of the bond between the electrophilic group and the PUG moiety.
  • Couplers which form cyan dyes upon reaction with oxidized color developing agents are described in such representative patents and publications as: U.S. Patent Nos. 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, "Farbkuppler-eine Literaturubersicht,” published in Agfa Mitannonen, Band III, pp. 156-175 (1961), and Section VII D of Research Disclosure, Item 308119, December 1989.
  • couplers are phenols and naphthols.
  • Couplers which form magenta dyes upon reaction with oxidized color developing agent are described in such representative patents and publications as: U.S. Patent Nos. 2,600,788; 2,369,489; 2,343,703; 2,311,082; 3,152,896; 3,519,429; 3,062,653; 2,908,573, "Farbkuppler-eine Literaturubersicht,” published in Agfa Mitannonen, Band III, pp. 126-156 (1961), and Section VII D of Research Disclosure, Item 308119, December 1989.
  • couplers are pyrazolones or pyrazolotriazoles.
  • Couplers which form colorless products upon reaction with oxidized color developing agent are described in such representative patents as: U.K. Patent No. 861,138; U.S. Patent Nos. 3,632,345; 3,928,041; 3,958,993 and 3,961,959.
  • couplers are cyclic carbonyl-containing compounds which react with oxidized color developing agents but do not form dyes.
  • R 2a , R 2d , R 2h , R 2i , R 2j , R 2k , R 2q and R 2r may also be a substituted or unsubstituted heterocyclic group selected from groups such as pyridine, pyrrole, furan, thiophene, pyrazole, thiazole, imidazole, 1,2,4-triazole, oxazole, thiadiazole, indole, benzthiophene, benzimidazole, benzoxazole and the like wherein the substitutents are as selected from those mentioned previously.
  • Suitable azo, azamethine and methine dyes are represented by the formulae in U.S. Patent No. 4,840884, col. 8, lines 1-70.
  • Y and Z are each preferably an aromatic group or an unsaturated heterocyclic group.
  • aromatic group a substituted or unsubstituted phenyl or naphthyl group is preferred.
  • unsaturated heterocyclic group a 4- to 7-membered heterocyclic group containing at least one hetero atom selected from a nitrogen atom, a sulfur atom and an oxygen atom is preferred, and it may be part of a benzene-condensed ring system.
  • the heterocyclic group means groups having a ring structure such as pyrrole, thiophene, furan, imidazole, 1,2,4-triazole, oxazole, thiadiazole, pyridine, indole, benzthiophene, benzimidazole, or benzoxazole.
  • Z is a substituted aryl group or a substituted unsaturated heterocyclic group
  • groups listed as substituents for Y can be used in the same manner for Z.
  • Couplers released can be nondiffusible color-forming couplers, non-color forming couplers or diffusible competing couplers.
  • Representative patents and publications describing competing couplers are: "On the Chemistry of White Couplers," by W. Puschel, Agfa-Gevaert AG Mitteilungen and der Anlagen Anlagen-Laboratorium der Agfa-Gevaert AG, Springer Verlag, 1954, pp. 352-367; U.S. Patent Nos. 2,998,314; 2,808,329; 2,689,793; 2,742,832; German Patent No. 1,168,769 and British Patent No. 907,274.
  • R 5c is hydrogen or alkyl of 1 to 4 carbon atoms and R 5d , R 5e , R 5f , R 5g , and R 5h are individually hydrogen, alkyl of 1 to 4 carbon atoms such as methyl or ethyl; hydroxyalkyl of 1 to 4 carbon atoms such as hydroxymethyl or hydroxyethyl or sulfoalkyl containing 1 to 4 carbon atoms.
  • R 7a is hydrogen, alkyl, such as methyl, ethyl, and butyl, alkoxy, such as ethoxy and butoxy, or alkylthio, such as ethylthio and butylthio, for example containing 1 to 6 carbon atoms, and which may be unsubstituted or substituted;
  • R 7b is hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl, such as phenyl;
  • R 7c , R 7d , R 7e and R 7f are individually hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl, such as straight chained or branched alkyl containing 1 to 6 carbon atoms, for example methyl, ethyl and butyl;
  • s is 1 to 6;
  • R 7c and R 7d , or R 7e and R 7f together may form a 5-,
  • R 7a and R 7b are solubilizing functions by the structure: where R 7c , R 7d , R 7e , R 7f , and s are as defined above.
  • the group represented by the above formula is a group capable of being oxidized by the oxidation product of a developing agent. More specifically, the sulfonamido group thereon is oxidized to a sulfonylimino group from which a development inhibitor is cleaved.
  • a layer or unit affected by PUG can be controlled by incorporating in appropriate locations in the element a layer that confines the action of PUG to the desired layer or unit.
  • at least one of the layers of the photographic element can be, for example, a scavenger layer, a mordant layer, or a barrier layer. Examples of such layers are described in, for example, U.S. Patent Nos. 4,055,429; 4,317,892; 4,504,569; 4,865,946; and 5,006,451.
  • the element can also contain additional layers such as antihalation layers, filter layers and the like.
  • the element typically will have a total thickness, excluding the support, of from 5 to 30 m.
  • the elements of this invention can contain brighteners (Section V), antifoggants and stabilizers (Section VI), antistain agents and image dye stabilizers (Section VII I and J), light absorbing and scattering materials (Section VIII), hardeners (Section X), coating aids (Section XI), plasticizers and lubricants (Section XII), antistatic agents (Section XIII), matting agents (Section XVI), and development modifiers (Section XXI), all in Research Disclosure, December 1989, Item 308119.
  • the color photographic elements of this invention can contain any of the optional additional layers and components known to be useful in color photographic elements in general, such as, for example, subbing layers, overcoat layers, surfactants and plasticizers, some of which are discussed in detail hereinbefore. They can be coated onto appropriate supports using any suitable technique, including, for example, those described in Research Disclosure, December 1989, Item 308117, Section XV Coating and Drying Procedures, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, PO9 1EF, U.K..
  • Imagewise exposures at ambient, elevated or reduced temperatures and/or pressures including high-or low-intensity exposures, continuous or intermittent exposures, exposure times ranging from minutes to relatively short durations in the millisecond to microsecond range and solarizing exposures, can be employed within the useful response ranges determined by conventional sensitometric techniques, as illustrated by T. H. James, The Theory of the Photographic Process, 4th Ed., Macmillan, 1977, Chapters 4, 6, 17, 18 and 23.
  • a 2030 mL solution containing 1.75% by weight low methionine gelatin (gelatin that has been treated with an oxidizing agent to reduce its methionine content to less than 30 micromoles per gram), 0.011 M sodium chloride and 1.48 x 10 -4 M potassium iodide was provided in a stirred reaction vessel.
  • the contents of the reaction vessel were maintained at 40°C and the pCl was 1.95.
  • each of the image-forming units can comprise a single radiation-sensitive layer, or each can independently include two (slow, fast) or three (slow, medium, fast) silver halide emulsion layers of differing sensitivity.
  • a tabular silver chloride emulsion containing grains bounded by ⁇ 100 ⁇ major faces can be located in the blue-sensitized silver halide emulsion unit only, or it can be in each of the units. Where a unit comprises more than one radiation-sensitive layer, the tabular silver chloride emulsion can be in the layer of lowest sensitivity, or in other or all of the layers in the unit.
  • Elements of the present invention having the layer order shown in Structure III can contain tabular silver chloride emulsions having grains bounded by ⁇ 100 ⁇ major faces in the slow emulsion layer of the yellow dye image-forming unit, as well as in the faster emulsion layers of this unit.
  • Tabular silver halide emulsions can also be employed in the layers of lowest sensitivity in the green- and/or red-sensitized emulsion units, as well as in all of the other radiation; sensitive layers of the element.
  • Structure IVa A variant of Structure IVa is Structure IVb (not shown), in which the positions of the slower and the fast silver halide emulsion layers are transposed in both the red-sensitized and in the green-sensitized emulsion units; i.e., the positions of the slower and the fast green-sensitized emulsion layers are reversed from their positions in Structure IVa, as are the positions of the red-sensitized emulsion layers.
  • the emulsions with tabular ⁇ 100 ⁇ -faced silver chloride grains can be situated in the overlying slower layers in the green- and red-sensitized silver halide emulsion units, or they can be utilized in all of the radiation-sensitive layers of the element.
  • the color photographic elements exhibited an unexpectedly high level of image sharpness. This image sharpness is sufficiently striking to be evident upon simple observation of the processed elements. Such sharpness is believed to be attributable to the unique morphology of the tabular ⁇ 100 ⁇ silver halide grains which provides refractive index values that are very close to those of the dispersing medium present in the emulsion layers.
  • the cubic silver chloride control emulsions whose grains have predominantly ⁇ 100 ⁇ faces, were prepared according to procedures described in U.S. Patent No. 4,952,491 and in Section I of Research Disclosure, Item 308119, December 1989. These emulsions were sensitized to green, blue, or red light by methods known in the art.
  • the cubic silver iodobromide emulsions were prepared by the procedures contained in Section I of Research Disclosure, Item 308119, December 1989. Sensitization was carried out by methods known in the art.
  • Solution 1 was charged into a reaction vessel equipped with a stirrer.
  • Solution 2 was added to the reaction vessel. While the mixture, which was at a pH of 6.0 and a temperature of 40C, was vigorously stirred, Solution 3 and Solution 4 were added at 80 mL/min. for 0.5 minute. The VAg was adjusted to 175 mV, and the mixture was held for ten minutes. Following this hold, Solution 3 and Solution 4 were added simultaneously at 24 mL/in. for 40 minutes; then the flow was linearly accelerated from 24 mL/min. to 48 mL/min. over 130 minutes, while the VAg was maintained at 175 mV. Solution 5 was added and stirred for 5 minutes.
  • the liquid layer was decanted, and the depleted volume was restored with distilled water.
  • the pH was adjusted to 4.5, and the mixture was held at 40C for 20 minutes before the pH was adjusted to 3.8 and the settling and decanting steps were repeated.
  • Solution 8 was added, and the pH and pCl were adjusted to 5.6 and 1.6, respectively.
  • the resulting emulsion contained tabular silver chloride grains having predominantly ⁇ 100 ⁇ faces, and average equivalent circular diameter (ECD) of 1.4 m, and an average thickness of 0.14 m.
  • ECD average equivalent circular diameter
  • the mixture was then held for 5 minutes; 7000 mL of distilled water was added and the temperature was raised to 65°C, while the pCl was adjusted to 2.15 and the pH to 6.5. Following the hold, the size of the resulting grains was increased through growth using a dual-zone process.
  • a solution of 0.67 M silver nitrate was premixed with a 0.67 M solution of sodium chloride and a solution of 0.5 percent by weight bone gelatin at a pH of 6.5, in a well-agitated continuous reactor with a total volume of 30 mL.
  • the effluent from this premixing reactor was then added to the original reaction vessel, which during this step acted as a growth reactor.
  • the fine crystals from the continuous reactor were ripened onto the original crystals through Ostwald ripening.
  • the total suspension volume of the growth reactor during this growth step was maintained constant at 13.5 L using ultrafiltration.
  • Sample 101 was prepared by applying the following layers to a clear support in the order indicated. Quantities of components are expressed in grams per square meter.
  • Layer 1 antihalation layer
  • Layer 2 light sensitive layer
  • Layer 3 protecting layer
  • Layer 3 comprising 2.15 g of gelatin.
  • Sample 107 was prepared like sample 101 except that emulsion EM-1c was replaced by an equal quantity of emulsion EM-6c.
  • Sample 108 was prepared like sample 101 except that emulsion EM-1c was replaced by an equal quantity of emulsion EM-7.
  • Sample 110 was prepared like sample 101 except that emulsion EM-1c was replaced by an equal quantity of emulsion EM-9c and image dye-forming coupler C-1 was replaced by 1.08 g of image dye-forming coupler C-3.
  • Samples 101-112 were exposed to white light through a graduated density test object and processed using the KODAK C-41 process.
  • the process was modified in that the bleach solution comprised ferric propylenediamine-tetraacetate.
  • the photographic sensitivity was measured as the exposure required to enable a Status M density of 0.15 above Dmin after processing.
  • the Status M density at a Dmax value was also measured.
  • Table 6 lists for each sample: the emulsion identity; surface area per grain; color sensitization; dye image-forming coupler; the experimentally observed relative sensitivity; the relative sensitivity expected assuming that, for a spectrally sensitized emulsion, the sensitivity is a linear function of grain surface area; and the Status M dye density formed at Dmax per gram of coupler coated per square meter per gram of silver per square meter in each sample, i.e., the normalized dye-density yield (DDY). Sensitivity and dye yield in a color process.
  • control samples 101, 102 and 103 illustrate the difficulty of achieving either high photographic sensitivity or high values of dye-density yield with cubic shaped ⁇ 100 ⁇ AgCl grains.
  • grain size and surface area
  • photographic sensitivity hardly increases at all while dye density yield falls dramatically.
  • the photographic sensitivity would be expected to increase directly as a function of surface area per grain for spectrally sensitized emulsions, this expectation was not fulfilled for the control samples.
  • samples 104 and 105 of the invention showed photographic sensitivity greatly exceeding that expected based on relative grain surface area.
  • the dye density yield achieved in these samples exceeded that available from even less photographically sensitive control samples.
  • Control samples 201 through 205 were prepared by applying the following layers to a clear support in the order indicated. Quantities of components are expressed in grams per square meter.
  • Layer 1 antihalation layer
  • Layer 2 light sensitive layer
  • Layer 3 protecting layer
  • Layer 3 comprising 2.15 g of gelatin.
  • Control samples 301 through 303 were prepared like samples 201 - 205, except that emulsion EM-13c was replaced by an equal weight of emulsion EM-6c.
  • Control samples 307 through 311 were prepared like samples 201 - 205, except that emulsion EM-13c was replaced by an equal weight of emulsion EM-12c.
  • Samples 201 through 329 were exposed to light through a graduated density test object and processed as color negative films according to the KODAK C-41 process.
  • the process was modified in that the bleach solution comprised ferric propylenediamine-tetraacetate.
  • Samples 901 through 969 were prepared generally as described for sample 101 of Example 2. All of these samples were coated on a transparent support. Samples 970 through 972 were coated on a reflective support. All of these elements represent further illustrations of the practice of this invention.
  • the identification and quantity of the silver halide emulsion and the identification and quantity of the image dye-forming and PUG-releasing coupler compounds employed in each sample are provided in Table 8 below.
  • Table 8 shows the identity and quantity of the emulsion and coupler compounds employed in each element.
  • the normalized dye density yield (DDY) observed for each sample and the wavelength band employed (R, G or B) is also shown.
  • Normalized dye density (DDY) from processed samples. Quantities of couplers and other compounds are listed in grams per meter squared.
  • Samples 901 through 969 were exposed to white light through a graduated density test object and developed for 45 seconds in the color paper developer described in U.S. Patent No. 4,892,804, then bleached and fixed. Good dye density formation from these elements was again observed.
  • Samples 401 through 412 were prepared by applying the following layers to a clear support in the order indicated. Quantities of components are expressed in grams per square meter.
  • Layer 1 antihalation layer
  • Layer 2 light sensitive layer
  • Layer 3 protecting layer
  • Layer 3 comprising 2.15 g of gelatin.
  • the layers additionally comprised alpha-4-nonylphenyl-omega-hydroxy-poly(oxy-(2-hydroxy-1,3-propanediyl)) and (para-t-octylphenyl)-di(oxy-1,2-ethanediyl)-sulfonate as surfactants.
  • Samples 401 through 412 were exposed to sinusoidal patterns of white light to determine the Modulation Transfer Function (MTF) Percent Response as a function of spatial frequency in the film plane.
  • the samples were then processed using the KODAK C-41 process.
  • the bleach used in the process was modified to comprise 1,3-propylenediamine-tetraacetic acid.
  • the exposed and processed elements were evaluated to determine the MTF Percent Response as a function of spatial frequency in the film plane. Specific details of this exposure - evaluation cycle can be found at R. L. Lamberts and F. C. Eisen, "A System for the Automatic Evaluation of Modulation Transfer Functions of Photographic Materials", in the Journal of Applied Photographic Engineering, vol. 6, pages 1-8, February 1980.
  • the MTF Percent Response of the light sensitive layers of these samples was monitored at several spatial frequencies. Higher values for MTF Percent Response indicate a sharper image. Additionally, the spatial frequency at which the MTF Percent Response dropped to 70%, which is a measure of resolving power, was determined. Higher spatial frequencies indicate a film with superior resolving power. The results of this test are also listed in Table 9.
  • elements of the invention containing a variety of DIR compounds all exhibited enhanced sharpness and generally improved resolving power.
  • the specific spatial frequencies enhanced and the degree of enhancement varies with the choice of dye image-forming and DIR coupler compounds. Combinations suitable for specific applications are readily ascertained by those skilled in the art.
  • Samples 501 through 504 were prepared by applying the following layers to a clear support in the order indicated. Quantities of components are expressed in grams per square meter.
  • Layer 1 antihalation layer
  • Layer 2 light sensitive layer
  • Layer 3 protection layer
  • Layer 3 comprising 2.15 g of gelatin.
  • the layers additionally comprised alpha-4-nonylphenyl-omega-hydroxy-poly(oxy-(2-hydroxy-1,3-propanediyl)) and (para-t-octylphenyl)-di(oxy-1,2-ethanediyl)-sulfonate as surfactants.
  • Samples 501 through 504 were exposed to white light through a graduated density test object, then processed using the KODAK C-41 process.
  • the bleach used in the process was modified to comprise 1,3-propylenediamine-tetraacetic acid.
  • the relative photographic sensitivities of the samples were then evaluated by determining the exposure required to produce a density of 0.15 above Dmin at a normalized gamma of 1.0.
  • Samples 505 through 511 were prepared in a manner similar to that used to prepare sample 501 of Example 6, except that the quantity and identity of the bleach accelerator-releasing (BAR) compound indicated in Table 11 was added to the light sensitive layer. Development inhibitor-releasing (DIR) compounds were also added to some samples to further illustrate the practice of the invention.
  • BAR bleach accelerator-releasing
  • DIR Development inhibitor-releasing
  • Samples 512 and 513 were prepared in a manner similar to that used to prepare sample 501 of Example 6, except that the quantities and identities of competing coupler releasing (CCR) compounds indicated in Table 12 were added to the light sensitive layer.
  • CCR competing coupler releasing
  • the layers additionally comprised alpha-4-nonylphenyl-omega-hydroxy-poly(oxy-(2-hydroxy-1,3-propanediyl)) and (para-t-octylphenyl)-di(oxy-1,2-ethanediyl)-sulfonate as surfactants.
  • Samples 514 and 515 were exposed to white light through a graduated density test object and processed using the KODAK C-41 process.
  • the bleach used in the process was modified to comprise 1,3-propylenediamine-tetraacetic acid.
  • the relative sensitivities, gammas, and maximum densities of the processed elements were determined. These values are reported in Table 13. Effect on photographic sensitivity, gamma and density formation produced by electron transfer agent releasing (ETAR) compound.
  • ETAR compound improved the sensitivity, density, and gamma of the element of the invention containing it.
  • ETAR compounds can also be used in combination with other PUG-releasing compounds described elsewhere herein.
  • Sample 516 was prepared in a manner similar to that used to prepare sample 501 of Example 6, except that the quantity and identity of the bleach inhibitor releasing compound indicated in Table 14 was added to the light sensitive layer.
  • the BIR compound retarded bleaching in the processed element containing it, thereby enabling the imagewise formation of IR-readable density, which can be employed for applications such as motion picture sound tracks.
  • BIR compounds can also be used in combination with other PUG-releasing compounds described herein.
  • the organic compounds were employed as used as emulsions containing coupler solvents, surfactants and stabilizers or as solutions, both as commonly employed in the art.
  • the coupler solvents employed in this photographic sample included: tricresylphosphate; di-n-butyl phthalate; N,N-di-n-ethyl lauramide; N,N-di-n-butyl lauramide; 2,4-di-t-amylphenol; N-butyl-N-phenyl acetamide; and 1,4-cyclohexylenedimethylene bis-(2-ethoxyhexanoate).
  • Mixtures of compounds were employed as individual dispersions or as co-dispersions as commonly practiced in the art.
  • the sample additionally comprised sodium hexametaphosphate, disodium 3,5-disulfocatechol, aurous sulfide, propargyl-aminobenzoxazole and so forth.
  • the silver halide emulsions were stabilized with 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene.
  • Layer 2 ⁇ Lowest Sensitivity Red-Sensitized Layer ⁇ : Red sensitized silver chloride cubic emulsion, average edge length 0.28 m at 0.215 g; Red sensitized silver chloride 100-faced tabular emulsion, average equivalent circular diameter 1.2 m, average grain thickness 0.14 m at 0.592 g; C-1 at 0.70 g; D-3 at 0.075; with gelatin at 2.04 g.
  • Layer 3 Highest Sensitivity Red-Sensitized Layer ⁇ : Red sensitized silver chloride 100-faced tabular emulsion, average equivalent circular diameter 1.4 m, average grain thickness 0.14 m at 0.538 g; C-1 at 0.129 g; D-15 at 0.032 g; with gelatin at 2.15 g.
  • Green sensitized silver chloride cubic emulsion Green sensitized silver chloride cubic emulsion, average edge length 0.28 m at 0.215 g; green sensitized silver chloride 100-faced tabular emulsion, average equivalent circular diameter 1.2 m, average grain thickness 0.14 m at 0.592 g; C-2 at 0.323 g; D-17 at 0.022 g; with gelatin at 1.72 g.
  • Layer 9 Highest Sensitivity Blue-Sensitized Layer ⁇ : Blue sensitized silver chloride 100 faced tabular emulsion, average equivalent circular diameter 1.4 m, average grain thickness 0.14 m at 0.323 g; C-3 at 0.129 g; D-18 at 0.043 g; with gelatin at 1.72 g.
  • This film was hardened at coating with 2% by weight to total gelatin of bis-vinylsulfonylmethane.
  • Surfactants, coating aids, scavengers, soluble absorber dyes and stabilizers were added to the various layers of this sample as is commonly practiced in the art.
  • the total dry thickness of the light sensitized layers was about 13.7 m and the total dry thickness of all the applied layers was about 19.5 m.
  • Sample ML-102 was like sample ML-101 except that compound B-1 was added to layer 2 at 0.043 g.
  • Sample ML-105 was like sample ML-104 except that compound B-1 was added to layer 2 at 0.043 g.
  • Sample ML-107 was like sample ML-104 except that the quantity of silver chloride emulsions in layers 2, 3, 5 and 6 was doubled and the quantities of compounds D-1 and D-4 in these layers was also doubled.
  • Samples ML-201-205 and ML-207-208 were prepared analogously to samples ML-101-105 and ML-107-108, except that the silver chloride emulsions were replaced in the light sensitive layers by sensitized silver iodobromide emulsions comprising about 3.7 mole percent iodide as follows: in Layer 2: Red sensitized silver iodobromide emulsion average equivalent circular diameter 0.5 m, average thickness 0.08 m at 0.215 g; Red sensitized silver iodobromide emulsion, average equivalent circular diameter 1.0 m, average grain thickness 0.09 m.
  • the density producing ability of multilayer, multicolor elements of the invention generally equaled or exceeded that of otherwise similar control samples that contain silver iodobromide emulsions. Additionally, the elements prepared in accordance with the invention produced more uniform density production in the three color records than did the control samples. This greater uniformity in density formation is presumably attributable to improved development in the underlying red-sensitized layers in the elements of the invention relative to those in the control elements. This decreased dependence of dye density formation in a particular layer on the position of that layer in the element is an important benefit of the invention.
  • Both pressured and unpressured portions of each sample were exposed to white light through a graduated density test object.
  • the samples were then processed using the KODAK C-41 process.
  • the bleach used in the process was modified to comprise 1,3-propylenediamine-tetraacetic acid.
  • the magnitude of the pressure-fog effect was quantified by comparing the blue Status M Dmin of an unpressured portion of each sample to that of a pressured portion of the same sample.
  • the increase in density caused by the abrasive wheel is the pressure-fog or photo-abrasion.
  • Smaller values of pressure-fog are superior in that they indicate that a particular film composition is less susceptible to forming unsightly marks and blemishes due, for example, to dirt or to imperfections in film transport apparatus during use. This indicates improved quality for prints made from such a color film.
  • the samples prepared according to the invention showed little pressure-desensitization and exhibited greatly improved resistance to photo-abrasion when compared to control samples employing similarly sized silver iodobromide emulsions.
  • Photographic samples ML-102 and ML-103 were exposed to light through a graduated density test object and a KODAK WRATTEN 29 filter. This arrangement enables a red-light separation exposure.
  • the samples were then processed using the KODAK C-41 process.
  • the bleach used in the process was modified to comprise 1,3-propylenediamine-tetraacetic acid
  • the change in green Status M density as a function of red-light exposure between Dmin and Dmax was measured This change in green densitv is shown in Table 17. Change in green density as a function of red-light exposure.
  • Sample ML-103 which incorporates the masking coupler, showed improved color separation properties; the undesired green density associated with exposure and development of the red light sensitized layers was reduced by the presence of the masking coupler C-42 in sample ML-103.
  • Photographic samples ML-102 and ML-103 were exposed to light through a graduated density test object and a KODAK WRATTEN 74 filter. This arrangement enables a green-light separation exposure.
  • the samples were then processed using the KODAK C-41 process.
  • the bleach used in the process was modified to comprise 1,3-propylenediamine-tetraacetic acid.
  • the change in blue Status M density as a function of green-light exposure between Dmin and Dmax was measured. This change in blue density is listed in Table 18. Change in blue density as a function of green-light exposure.
  • Photographic sample ML-101 was exposed to white light through a graduated density test object and processed according to the KODAK E-6 reversal film process.
  • a reversal image suitable for direct viewing was formed.
  • a color photographic element sample ML-301, was prepared by applying the following layers in the given sequence to a transparent support of cellulose triacetate.
  • the quantities of silver halide are given in g of silver per m 2 .
  • the quantities of other materials are given in g per m 2 .
  • the organic compounds were used as emulsions containing coupler solvents, surfactants and stabilizers or as solutions both as commonly employed in the art.
  • the coupler solvents employed in this photographic sample included: tricresylphosphate; di-n-butyl phthalate; N,N-di-n-ethyl lauramide; N,N-di-n-butyl lauramide; 2,4-di-t-amylphenol; N-butyl-N-phenyl acetamide; and 1,4-cyclohexylenedimethylene bis-(2-ethoxyhexanoate).
  • Mixtures of compounds were employed as individual dispersions or as co-dispersions as commonly practiced in the art.
  • the sample additionally comprised sodium hexametaphosphate, disodium 3,5-disulfocatechol, aurous sulfide, propargyl-aminobenzoxazole and so forth.
  • the silver halide emulsions were stabilized with 2 grams of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene per mole of silver.
  • Layer 2 ⁇ Lowest Sensitivity Red-Sensitized Layer ⁇ : Red sensitized silver iodobromide emulsion, ca.
  • Layer 9 Highest Sensitivity Blue-Sensitized Layer ⁇ : Blue sensitized silver iodobromide emulsion, ca. 9 mole percent iodide, average equivalent circular diameter 1.3 m at 0.646 g; C-3 at 0.129 g; D-8 at 0.043 g; with gelatin at 1.72 g.
  • Layer 10 ⁇ Protective Layer-1 ⁇ : DYE-8 at 0.108 g; DYE-9 at 0.161 g; unsensitized silver bromide Lippman emulsion at 0.108 g; N,N,N-trimethyl-N-(2-perfluoro-octylsulfonamido-ethyl) ammonium iodide; sodium tri-isopropylnaphthalene sulfonate; and gelatin at 0.54 g.
  • Layer 11 Protective Layer-2 ⁇ : silicone lubricant at 0.026 g; tetraethylammonium perfluoro-octanesulfonate; t-octylphenoxyethoxyethylsulfonic acid sodium salt; anti-matte polymethylmethacrylate beads at 0.0538 g; and gelatin at 0.54 g.
  • Sample ML-302 was like sample ML-301 except that the silver iodobromide emulsions were removed from layers 8 and 9 and replaced with equal weights of silver chloride emulsions as follows: to Layer 8: cubic blue sensitized silver chloride emulsion, average edge length 0.28 m, at 0.43 g. to Layer 9: cubic blue sensitized silver chloride emulsion, average edge length 0.6 m at 0.646 g.
  • Photographic sample ML-303 was like photographic sample ML-301 except that the silver iodobromide emulsions were removed from layers 8 and 9 and replaced with equal weights of silver chloride emulsions as follows: to Layer 8: ⁇ 100 ⁇ -faced tabular blue sensitized silver chloride emulsion, average equivalent circular diameter 1.2 m, average grain thickness 0.14 m at 0.43 g. to Layer 9: ⁇ 100 ⁇ -faced tabular blue sensitized silver chloride emulsion, average equivalent circular diameter 1.4 m, average grain thickness 0.14 m at 0.646 g.
  • Samples ML-301, ML-302 and ML-303 were exposed to sinusoidal patterns of white light to determine the Modulation Transfer Function (MTF) Percent Response as a function of spatial frequency in the film plane.
  • the samples were then processed using the KODAK C-41 process.
  • the bleach used in the process was modified to comprise 1,3-propylenediamine-tetraacetic acid.
  • the exposed and processed samples were evaluated to determine the MTF Percent Response as a function of spatial frequency in the film plane. Specific details of this exposure - evaluation cycle can be found in R. L. Lamberts and F. C. Eisen, "A System for the Automatic Evaluation of Modulation Transfer Functions of Photographic Materials", in the Journal of Applied Photographic Engineering, vol 6, pages 1-8, February 1980. A more general description of the determination and meaning of MTF Percent Response curves can be found in the articles cited within this reference.
  • Samples ML-301 through ML-303 are identical except for the morphology and iodide content of the emulsions incorporated in the blue light sensitized layers.
  • the blue light sensitized layer is closer to an exposure source than are the green light or red light sensitized layers.
  • Incorporation of sensitized ⁇ 100 ⁇ -faced tabular AgCl emulsions in the blue light sensitized layers in accordance with the present invention greatly improved the resolving power of the underlying layers, as can be seen by comparison with the results from the control elements containing either a cubic silver chloride emulsion or a tabular silver iodobromide emulsion in the overlying blue sensitized layers.
  • the MTF percent response at low spatial frequencies is also greatly improved.
  • a color photographic element sample ML-401, was prepared by applying the following layers in the given sequence to a transparent support of cellulose triacetate.
  • the quantities of silver halide are given in g of silver per m 2 .
  • the quantities of other materials are given in g per m 2 .
  • the organic compounds were used as emulsions containing coupler solvents,surfactants and stabilizers or as solutions both as commonly employed in the art.
  • the coupler solvents employed in this photographic sample included: tricresylphosphate; di-n-butyl phthalate; N,N-di-n-ethyl lauramide; N,N-di-n-butyl lauramide; 2,4-di-t-amylphenol; N-butyl-N-phenyl acetamide; and 1,4-cyclohexylenedimethylene bis-(2-ethoxyhexanoate).
  • Mixtures of compounds were employed as individual dispersions or as co-dispersions as commonly practiced in the art.
  • the sample additionally comprised sodium hexametaphosphate, disodium 3,5-disulfocatechol, aurous sulfide, propargyl-aminobenzoxazole and so forth.
  • the silver halide emulsions were stabilized with 2 grams of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene per mole of silver.
  • Layer 8-(SM) ⁇ Lowest Sensitivity Green-Sensitized Layer ⁇ : Green sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion, average equivalent circular diameter 1.2 m, average grain thickness 0.12 m at 0.807 g; magenta dye-forming image coupler C-2 at 0.323 g; D-17 at 0.065 g; with gelatin at 2.15 g.
  • This film was hardened at coating with 2% by weight to total gelatin of bis-vinylsulfonylmethane.
  • Surfactants, coating aids, scavengers, soluble absorber dyes and stabilizers were added to the various layers of this sample as is commonly practiced in the art.
  • the total dry thickness of the light sensitized layers was about 10.5 m while the total dry thickness of all of the applied layers was about 16.8 m.
  • the layer order sequence of sample ML-401 was thus: support, AHU, SY, FY, IL, SC, FC, IL, SM, FM, OC.
  • Sample ML-402 was like sample ML-401 except that compound C-40 was added to layer 8-(SM) at 0.065 g and to layer 9-(FM) at 0.043 g.
  • Sample ML-404 was prepared by applying the layers employed in sample 401 to the support in the sequence AHU, SC, FC, IL, SM, FM, IL, SY, FY, OC, as follows: Layer 1-(AHU) ⁇ Antihalation Layer ⁇ : DYE-1 at 0.043 g; DYE-2 at 0.021 g; C-39 at 0.065 g; DYE-6 at 0.215 g; with 2.15 g gelatin.
  • Layer 6-(FM) Highest Sensitivity Green-Sensitized Layer ⁇ : Green sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion, average equivalent circular diameter 1.4 m, average grain thickness 0.14 m at 0.538 g; magenta dye-forming image coupler C-2 at 0.086 g; D-16 at 0.032 g, with gelatin at 1.72 g.
  • Layer 9-(FY) ⁇ Highest Sensitivity Blue-Sensitized Layer ⁇ Blue sensitized silver chloride ⁇ 100 ⁇ faced tabular emulsion, average equivalent circular diameter 1.4 m, average grain thickness 0.14 m at 0.646 g; yellow dye-forming image coupler C-3 at 0.129 g; D-18 at 0.086 g; with gelatin at 1.72 g.
  • Sample ML-405 was like sample ML-404 except that compound C-42 was added to layer 2-(SC) at 0.065 g and layer 3-(FC) at 0.043 g; and compound C-40 was added to layer 5-(SM) at 0.065 g and layer 6-(FM) at 0.043 g.
  • Samples ML-401 through ML-403 were exposed to light through a graduated density test object and a KODAK WRATTEN 74 filter. This arrangement enables a green-light separation exposure.
  • the samples were then processed using the KODAK C-41 process.
  • the bleach used in the process was modified to comprise 1,3-propylenediamine-tetraacetic acid.
  • the change in blue Status M density as a function of green-light exposure between a Dmin and Dmax was measured. This change in blue density is listed in Table 20, below.
  • the samples were additionally exposed to white light through a graduated density test object and the relative blue light sensitivity of the blue light sensitized layer monitored. These values are also listed in Table 20.
  • Samples ML-401 through ML-405 contain ⁇ 100 ⁇ -faced tabular silver iodobromide emulsion in all of the light sensitive layers.
  • Samples ML-404 and ML-405 have a normal layer order for color films incorporating silver iodobromide emulsions, i.e., the blue light sensitized layer is closer to the exposure source than are the green or red light sensitized layers.
  • This layer order is normal for silver iodobromide emulsion films because the silver iodobromide emulsions are all sensitive to blue light, and good color separation is best obtained when a yellow colored filter layer is interposed between the layers spectrally sensitized to green or red light and the exposure source.
  • Samples ML-401 through 403 employ an inverted layer order in which the emulsion layers spectrally sensitized to blue light are positioned further from the exposure source than are the emulsion layers spectrally sensitized to green or red light.
  • the resolving power of the red light sensitized layer is improved by removing the light scattering film components associated with the blue light sensitized layer from the exposure light path for the red sensitized layer. This is demonstrated as described below.
  • Samples ML-401 through ML-405 were exposed to sinusoidal patterns of white light to determine the Modulation Transfer Function (MTF) Percent Response as a function of spatial frequency in the film plane.
  • the samples were then processed using the KODAK C-41 process.
  • the bleach used in the process was modified so as to comprise 1,3-propylenediamine-tetraacetic acid.
  • the exposed and processed samples were evaluated to determine the MTF Percent Response as a function of spatial frequency in the film plane. Specific details of this exposure - evaluation cycle can be found in the previously mentioned paper by R. L. Lamberts and F. C. Eisen.
  • Samples ML-401 through ML-405 were evaluated for pressure-fog or photoabrasion sensitivity as previously described in example 11-C.
  • the organic compounds were used as emulsions containing coupler solvents, surfactants and stabilizers or used as solutions both as commonly employed in the art.
  • the coupler solvents employed in this photographic sample included: tricresylphosphate; di-n-butyl phthalate; N,N-di-n-ethyl lauramide; N,N-di-n-butyl lauramide; 2,4-di-t-amylphenol; N-butyl-N-phenyl acetamide; and 1,4-cyclohexylenedimethylene bis-(2-ethoxyhexanoate).
  • Mixtures of compounds were employed as individual dispersions or as co-dispersions as commonly practiced in the art.
  • the sample additionally comprised sodium hexametaphosphate, disodium 3,5-disulfocatechol, aurous sulfide, propargyl-aminobenzoxazole and so forth
  • the silver halide emulsions were stabilized with 2 grams of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene per mole of silver.
  • Layer 2 ⁇ Lowest Sensitivity Red-Sensitized Layer ⁇ : Red sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion, average equivalent circular diameter 1.2 m, average grain thickness 0.12 m at 0.807 g; cyan dye-forming image coupler C-1 at 0.70 g; D-3 at 0.075; with gelatin at 2.04 g.
  • Layer 3 Highest Sensitivity Red-Sensitized Layer ⁇ : Red sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion, average equivalent circular diameter 1.4 m, average grain thickness 0.14 m at 0.538 g; cyan dye-forming image coupler C-1 at 0.129 g; D-15 at 0.048 g; with gelatin at 2.15 g.
  • Layer 4 ⁇ Interlayer ⁇ : 1.29 g of gelatin.
  • Green sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion, average equivalent circular diameter 1.2 m, average grain thickness 0.12 m at 0.807 g; magenta dye-forming image coupler C-2 at 0.323 g; D-17 at 0.065 g; with gelatin at 2.15 g.
  • Green-Sensitized Layer ⁇ Green sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion, average equivalent circular diameter 1.4 m, average grain thickness 0.14 m at 0.538 g; magenta dye-forming image coupler C-2 at 0.086 g; D-16 at 0.032 g, with gelatin at 1.72 g.
  • Layer 8 ⁇ Lowest Sensitivity Blue-Sensitized Layer ⁇ : Blue sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion, average equivalent circular diameter 1.2 m, average grain thickness 0.12 m at 0.43 g; yellow dye-forming image coupler C-3 at 1.08 g; D-18 at 0.108 g; with gelatin at 1.72 g.
  • Layer 9 ⁇ Highest Sensitivity Blue-Sensitized Layer ⁇ : Blue sensitized silver chloride ⁇ 100 ⁇ faced tabular emulsion, average equivalent circular diameter 1.4 m, average grain thickness 0.14 m at 0.646 g; yellow dye-forming image coupler C-3 at 0.129 g; D-18 at 0.086 g; with gelatin at 1.72 g.
  • Sample ML-502 was like sample ML-501 except that compound B-1 was added to layer 2 at 0.043 g.
  • Sample ML-503 was like sample ML-502 except that compound C-42 was added to layer 2 at 0.065 g and layer 3 at 0.043 g; and compound C-40 was added to layer 5 at 0.065 g and layer 6 at 0.043 g.
  • Sample ML-504 was like sample ML-501 except that compounds D-3, D-15 and D-18 were omitted and the following compounds added instead: to layer 2 add 0.075 g of D-4; to layer 3 add 0.048 g of D-1; to layer 8 add 0.108 g of D-7; and to layer 9 add 0.086 g of D-7.
  • Sample ML-505 was like sample ML-504 except that compound B-1 was added to layer 2 at 0.043 g.
  • Sample ML-507 was like sample ML-504 except that the quantity of silver chloride emulsions in layers 2, 3, 5 and 6 was doubled and the quantities of compounds D-1, D-4, D-16 and D-17 in these layers was also doubled These changes add about 1.1 m to the total dry thickness.
  • Sample ML-508 was like sample ML-501 except that the quantity of silver chloride emulsions in layers 2, 3, 5 and 6 was doubled and the quantities of compounds D-3, D-15, D-16 and D-17 in these layers was also doubled.
  • the samples were exposed to white light through a graduated density test object, then processed using the KODAK C-41 process.
  • the bleach used in the process was modified to comprise 1,3-propylenediamine-tetraacetic acid.
  • the Status M density produced in a Dmin area of each sample was measured after processing.
  • the Status M density produced after processing at an exposure level ten stops (i.e. 3.0 log E) higher than the ISO speed-point was measured.
  • the ISO speed-point is the exposure required to produce a Status M density 0.15 above Dmin.
  • the difference in density production between Dmin and Dmax was calculated by subtraction. The difference represents the useful imaging density range of each sample.
  • the Dmin or photographic fog density and the useful imaging density are shown in Table 23. Status M fog density and useful imaging density.
  • the useful imaging densities of multilayer, multicolor elements prepared according to the invention equaled or exceeded that of a comparative commercial 100 speed film sample that utilizes silver iodobromide emulsions, while the fog values were lower, resulting in improved image - fog discrimination. Additionally, the samples prepared in accordance with the invention produced more uniform density production in the three color records than does the commercial film sample.
  • Samples ML-502, ML-503, ML-505 and ML-506 were exposed light through a graduated density test object and a KODAK WRATTEN 29 filter. This arrangement enables a red-light separation exposure.
  • the samples were then processed using the KODAK C-41 process.
  • the bleach used in the process was modified to comprise 1,3-propylenediamine-tetraacetic acid
  • the change in green Status M density as a function of red-light exposure between a Dmin and Dmax was measured. This change in green density is shown in Table 24. Change in green density as a function of red-light exposure.
  • Samples ML-502, ML-503, ML-505 and ML-506 were exposed light through a graduated density test object and a KODAK WRATTEN 74 filter. This arrangement enables a green-light separation exposure.
  • the samples were then processed using the KODAK C-41 process.
  • the bleach used in the process was modified to comprise 1,3-propylenediamine- tetraacetic acid.
  • the change in blue Status M density as a function of green-light exposure between Dmin and Dmax was measured. This change in blue density is shown in Table 25. Change in blue density as a function of green-light exposure.
  • Samples ML-501, ML-502, ML-504, ML-505 were exposed to white light or to red light using a KODAK WRATTEN 29 filter through a graduated density test object The samples were then processed using the KODAK C-41 process.
  • the bleach used in the process was modified to comprise 1,3-propylenediamine-tetraacetic acid.
  • the gamma of the cyan image formed in the red light sensitized element of the samples under both exposure conditions was then determined.
  • the ratio of the red density gamma formed after a red light exposure divided by the red density gamma formed after a white light exposure is a measure of the onto red interimage effects caused by development inhibiting products of development released in the green light and blue light o sensitized elements during their development. These products are not released from the green and blue light sensitized layers in the case of a red light exposure and process but are released in the case of a white light exposure and process.
  • the development inhibiting products released are the development inhibitors released from the DIR compounds purposefully added to the green and blue light sensitized layers.
  • solubilized aliphatic thiol releasing compounds (compound B-1 is an example of such a solubilized thiol releasing compound) are known to interfere with the inhibition reaction between development inhibitors and of silver iodobromide emulsions.
  • the samples evaluated in this test differ only in the presence or absence of compound B-1 The results of this evaluation are shown in Table 26. Gamma ratio of red and white light exposures.
  • Samples ML-501, ML-504, ML-507, ML-508 and a commercial 100 speed color negative film containing silver iodobromide emulsions were exposed to white light or to red light using a KODAK WRATTEN 29 filter through a graduated density test object. The samples were then processed using the KODAK process. The bleach used in the process was modified to comprise 1,3-propylenediamine-tetraacetic acid.
  • the gamma of the cyan image formed in the red light sensitized element of the samples under both exposure conditions was then determined.
  • the ratio of the red density gamma formed after a red light exposure divided by the red density gamma formed after a white light exposure is a measure of the onto red interimage effects caused by development inhibiting products of development released in the green light and blue light sensitized elements during their development. These products are not released from the green and blue light sensitized layers in the case of a red light exposure and process but are released in the case of a white light exposure and process.
  • the development inhibiting products released are the development inhibitors released from the DIR compounds purposefully added to the green and blue light sensitized layers.
  • a color photographic element sample ML-601 was prepared by applying the following layers in the given sequence to a transparent support of cellulose triacetate.
  • the quantities of silver halide are given in g of silver per m 2 .
  • the quantities of other materials are given in g per m 2 .
  • Layer 1 Antihalation Layer ⁇ : DYE-1 at 0.011 g; DYE-2 at 0.013 g; C-39 at 0.065 g; DYE-6 at 0.108 g; DYE-9 at 0.075 g; gray colloidal silver at 0.215 g; SOL-1 at 0.005; SOL-2 at 0.005 g; with 2.41 g gelatin.
  • Layer 2 ⁇ Interlayer ⁇ : 0.108 g of S-1; with 1.08 g of gelatin.
  • Layer 3 ⁇ Lowest Sensitivity Red-Sensitized Layer ⁇ : Red sensitized silver iodobromide emulsion, ca.
  • Layer 10 ⁇ Interlayer ⁇ : S-1 at 0.054 g; DYE-9 at 0.108 g; DYE-7 at 0.108 g; with 1.29 g of gelatin.
  • Layer 11 ⁇ Lowest Sensitivity Blue-Sensitized Layer ⁇ : Blue sensitized silver iodobromide emulsion, ca. 4 mole percent iodide, average equivalent circular diameter 0.5 m, average grain thickness 0.08 at 0.172 g; Blue sensitized silver iodobromide emulsion, ca.
  • Layer 14 Protective Layer-2 ⁇ : silicone lubricant at 0.026 g; tetraethylammonium perfluoro-octane sulfonate; t-octylphenoxyethoxyethylsulfonic acid sodium salt; anti-matte polymethylmethacrylate beads at 0.0538 g; and gelatin at 0.91 g.
  • This film was hardened at coating with 2% by weight to total gelatin of bis-vinylsulfonylmethane.
  • Surfactants, coating aids, scavengers, soluble absorber dyes and stabilizers were added to the various layers of this sample as is commonly practiced in the art.
  • the total dry thickness of the light sensitized layers was about 15.1 m, while the total thickness of all the applied layers was about 23.1 m.
  • Sample ML-603 was like sample ML-601 except that the silver iodobromide emulsions in layers 11 and 12 (the two blue light sensitized layers) were replaced by equimolar quantities of ⁇ 100 ⁇ -faced tabular blue sensitized silver chloride emulsions, as follows: to layer 11 add a blue sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion with average equivalent circular diameter of 1.2 m and average grain thickness of 0.14 m at 0.344 g; to layer 12 add a blue sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion with average equivalent circular diameter of 1.4 m and average grain thickness of 0.14 m at 0.43 g.
  • Samples ML-601, ML-602 and ML-603 were exposed to sinusoidal patterns of white light to determine the Modulation Transfer Function (MTF) Percent Response as a function of spatial frequency in the film plane.
  • the samples were then processed using the KODAK C-41 process.
  • the bleach used in the process was modified to comprise 1,3-propylenediamine-tetraacetic acid.
  • the exposed and processed samples were evaluated to determine the MTF Percent Response as a function of spatial frequency in the film plane. Specific details of this exposure - evaluation cycle can be found in the previously mentioned paper by R. L. Lamberts and F. C. Eisen.
  • the front surface reflection of the film samples as a function of the wavelength of reflected light was also determined.
  • the quantity of light reflected at 600 nm from the front surface of a film sample can be important when the film is intended for use in an auto-exposure camera that utilizes a light reflection monitoring scheme to measure scene illuminance as part of the automatic exposure control sequence. These values are also reported in Table 28. Resolving power and percent reflected light at 600nm as a function of emulsion type in overlying layers.
  • Samples ML-601 through ML-603 are identical except for the morphology and iodide content of the emulsions incorporated in the blue light sensitized layers.
  • the blue light sensitized layer is closer to an exposure source that are the green light or red light sensitized layers.
  • Incorporation of sensitized ⁇ 100 ⁇ -faced tabular AgCl emulsions in the blue light sensitized layers in accordance with the present invention greatly improved the resolving power of the underlying layers, as can be seen by comparison with the results from the control elements containing either a cubic silver chloride emulsion or a tabular shaped silver iodobromide emulsion in the overlying blue sensitized layers.
  • Lowered front surface reflection also resulted from the use of the ⁇ 100 ⁇ -faced tabular AgCl emulsions.
  • a color photographic element sample ML-701, was prepared by applying the following layers in the given sequence to a transparent support of cellulose triacetate.
  • the quantities of silver halide are given in g of silver per m 2 .
  • the quantities of other materials are given in g per m 2 .
  • the organic compounds were used as emulsions containing coupler solvents, surfactants and stabilizers or used as solutions both as commonly practiced in the art.
  • the coupler solvents employed in this photographic sample included: tricresylphosphate; di-n-butyl phthalate; N,N-di-n-ethyl lauramide; N,N-di-n-butyl lauramide; 2,4-di-t-amylphenol; N-butyl-N-phenyl acetamide; and 1,4-cyclohexylenedimethylene bis-(2-ethoxyhexanoate).
  • Mixtures of compounds were employed as individual dispersions or as co-dispersions as commonly practiced in the art.
  • the sample additionally comprised sodium hexametaphosphate, disodium 3,5-disulfocatechol, aurous sulfide, propargyl-aminobenzoxazole and so forth.
  • the silver halide emulsions were stabilized with 2 grams of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene per mole of silver.
  • Layer 3 ⁇ Lowest Sensitivity Red-Sensitized Layer ⁇ : Red sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion, average equivalent circular diameter 1.2 m, average thickness 0.12 m at 0.538 g; C-1 at 0.538 g; D-15 at 0.011g; C-42 at 0.054 g; D-3 at 0.054 g; C-41 at 0.032 g; S-2 at 0.005 g; with gelatin at 1.72 g.
  • Layer 4 ⁇ Medium Sensitivity Red-Sensitized Layer ⁇ : Red sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion, average equivalent circular diameter 1.5 m, average grain thickness 0.14 m at 0.592 g; C-1 at 0.075 g; D-15 at 0.011 g; C-42 at 0.032 g; D-17 at 0.032 g; C-41 at 0.022 g; S-2 at 0.005 g; with gelatin at 1.72 g.
  • Layer 5 Highest Sensitivity Red-Sensitized Layer ⁇ : Red sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion, average equivalent circular diameter 2.2 m, average grain thickness 0.12 m at 0.592 g; C-1 at 0.075 g; D-15 at 0.011 g; C-42 at 0.022 g; D-17 at 0.032 g; C-41 at 0.011 g; S-2 at 0.005 g; with gelatin at 1.72 g.
  • Layer 6 ⁇ Interlayer ⁇ : S-1 at 0.054 g; D-25 at 0.032 g; with 1.08 g of gelatin.
  • Layer 7 ⁇ Lowest Sensitivity Green-Sensitized Layer ⁇ : Green sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion, average equivalent circular diameter 1.2 m, average grain thickness 0.12 m at 0.484 g; C-2 at 0.355 g; D-17 at 0.022 g; C-40 at 0.043 g; D-8 at 0.022 g; S-2 at 0.011 g; with gelatin at 1.13 g.
  • Green sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion, average equivalent circular diameter 1.5 m, average grain thickness 0.14 m at 0.592 g; C-2 at 0.086 g; D-17 at 0.022 g; C-40 at 0.038 g; S-2 at 0.011 g; with gelatin at 1.4 g.
  • Layer 9 Highest Sensitivity Green-Sensitized Layer ⁇ : Green sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion, average equivalent circular diameter 2.2 m, average grain thickness 0.12 m at 0.592 g; C-2 at 0.075 g; D-16 at 0.022 g; C-40 at 0.038 g; D-7 at 0.022 g; S-2 at 0.011 g; with gelatin at 1.35 g.
  • Layer 10 ⁇ Interlayer ⁇ : S-1 at 0.054 g; DYE-7 at 0.108 g; with 0.97 g of gelatin.
  • Layer 11 ⁇ Lowest Sensitivity Blue-Sensitized Layer ⁇ : Blue sensitized silver chloride cubic emulsion, average edge length 0.28 m, at 0.344 g; C-3 at 1.08 g; D-18 at 0.065 g; D-19 at 0.065 g; B-1 at 0.005 g; S-2 at 0.011 g; with gelatin at 1.34 g.
  • Layer 12 ⁇ Highest Sensitivity Blue-Sensitized Layer ⁇ : Blue sensitized silver chloride cubic emulsion, average edge length 0.6 m, at 0.43 g; C-3 at 0.108 g; D-18 at 0.043 g; B-1 at 0.005 g; S-2 at 0.011 g; with gelatin at 1.13 g.
  • Layer 13 ⁇ Protective Layer-1 ⁇ : DYE-8 at 0.054 g; DYE-9 at 0.108 g; DYE-10 at 0.054 g; unsensitized silver bromide Lippman emulsion at 0.108 g; N,N,N,-trimethyl-N-(2-perfluoro-octylsulfonamidoethyl) ammonium iodide; sodium tri-isopropylnaphthalene sulfonate; SOL-C1 at 0.043 g; and gelatin at 1.08 g.
  • Layer 14 Protective Layer-2 ⁇ : silicone lubricant at 0.026 g; tetraethylammonium perfluoro-octane sulfonate; t-octylphenoxyethoxyethylsulfonic acid sodium salt; anti-matte polymethylmethacrylate beads at 0.0538 g; and gelatin at 0.91 g.
  • This film was hardened at coating with 2% by weight to total gelatin of bis-vinylsulfonylmethane.
  • Surfactants, coating aids, scavengers, soluble absorber dyes and stabilizers were added to the various layers of this sample as is commonly practiced in the art.
  • the total dry thickness of the light sensitized layers was about 12.1 m while the total dry thickness of all the applied layers was about 20.5 m.
  • Sample ML-702 was like sample ML-701 except that the silver chloride cubic emulsions were omitted from in layers 11 and 12 (the two blue light sensitized layers) and replaced by equimolar quantities of ⁇ 100 ⁇ -faced tabular blue sensitized silver chloride emulsions, as follows: to layer 11 add a blue sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion with average equivalent circular diameter of 1.2 m and average grain thickness of 0.12 m at 0.172 g; and a blue sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion with average equivalent circular diameter of 1.5 m and average grain thickness of 0.14 m at 0.172 g; to layer 12 add a blue sensitized silver chloride ⁇ 100 ⁇ -faced tabular emulsion with average equivalent circular diameter of 2.2 m and average grain thickness of 0.12 m at 0.43 g.
  • Sample ML-704 was like sample ML-703 except that coupler C-2 was omitted from layers 7, 8 and 9 and replaced by coupler C-18, as follows: to layer 7 add 0.71 g of C-18; to layer 8 add 0.172 g of C-18; and to layer 9 add 0.151 g of C-18.
  • Sample ML-705 was like sample ML-703 except that coupler C-2 was omitted from layers 7, 8 and 9 and replaced by couplers C-15 and C-16, as follows: to layer 7 add 0.16 g of C-15 and 0.16 g of C-16; to layer 8 add 0.039 g of C-15 and 0.039 g of C-16; and to layer 9 add 0.033 g of C-15 and 0.033 g of C-16.
  • Sample ML-706 was like sample ML-703 except that coupler C-2 was omitted from layers 7, 8 and 9 and replaced by coupler C-15, as follows: to layer 7 add 0.32 g of C-15; to layer 8 add 0.077 g of C-15; and to layer 9 add 0.068 g of C-15.
  • Sample ML-707 was like sample ML-706 except that 0.006 g of DYE-2 was added to layer 13; 0.065 g of BA-1 was added to layer 1.
  • Sample ML1-708 was like sample ML-706 except that 0.006 g of DYE-2 was added to layer 13; 0.258 g of BA-2 was added to layer 1.
  • Samples ML-701 through ML-708 as well as a sample of a commercial 100 speed color negative film comprising silver iodobromide emulsions in the light sensitized layers were exposed to sinusoidal patterns of white light and then developed according to the Kodak C-41 Process.
  • the sinusoidal patterns were evaluated to determine the MTF percent response as described in Example 14.
  • Samples ML-701 through ML-708 as well as a sample of a commercial 100 speed color negative film comprising silver iodobromide emulsions in the radiation sensitive layers were exposed through the base to a spark discharge providing ultraviolet and visible light, then developed in the Kodak C-41 process with a modified bleach containing 1,3-propylenediamine-tetraacetic acid.
  • the relative speeds to white and ultraviolet light of the red layers of the elements employing silver chloride tabular emulsions in accordance with the invention and the control sample employing silver iodobromide emulsions were then compared.
  • the elements of the invention showed, when adjusted to comparable visible light sensitivity, a lowered sensitivity to ultraviolet light of about 100-fold (ca. 1-0 log E), indicative of spark and static discharge properties that are superior to those of the control sample.

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Claims (21)

  1. Farbfotografisches Element mit einem Träger, der mindestens eine strahlungsempfindliche Emulsionsschicht aufweist, die ein Dispergiermedium und Silberhalogenidkörner umfaßt und in reaktiver Assoziation eine einen Bildfarbstoff erzeugende Verbindung aufweist, in welchem
    (A) tafelförmigen Körnern, welche (a) durch {100}-Hauptflächen mit aneinandergrenzenden Kantenverhältnissen von weniger als 10 begrenzt sind, (b) jeweils ein Verhältnis Kreisäquivalentdurchmesser zu Dicke von mindestens 2 aufweisen und (c) innerlich an ihren Keimbildungsstellen lod und mindestens 50 Molprozent Chlorid enthalten, mindestens 50% der gesamten von Korn überragten Fläche ausmachen und
    (B) die Emulsionsschicht in reaktiver Assoziation auch eine Verbindung aufweist, die eine fotografisch nützliche Gruppe enthält und in der Lage ist, mit oxidiertem Entwicklungsmittel zu reagieren, um dadurch eine derartige Gruppe freizusetzen.
  2. Farbfotografisches Element nach Anspruch 1, in welchem das Verhältnis Kreisäquivalentdurchmesser zu Dicke mindestens 5 ist.
  3. Farbfotografisches Element nach Anspruch 2, in welchem das Verhältnis Kreisäquivalentdurchmesser zu Dicke größer als 8 ist.
  4. Farbfotografisches Element nach irgendeinem der Ansprüche 1 bis 3, in welchem die Kantenverhältnisse weniger als 5 betragen.
  5. Farbfotografisches Element nach Anspruch 4, in welchem die Kantenverhältnisse weniger als 2 betragen.
  6. Farbfotografisches Element nach irgendeinem der Ansprüche 1 bis 5, in welchem die tafelförmigen Körner eine Dicke von weniger als 0,3 µm aufweisen.
  7. Farbfotografisches Element nach Anspruch 6, in welchem die tafelförmigen Körner eine Dicke von weniger als 0,2 µm aufweisen.
  8. Farbfotografisches Element nach Anspruch 7, in welchem die tafelförmigen Körner eine Dicke von weniger als 0,06 µm aufweisen.
  9. Farbfotografisches Element nach irgendeinem der Ansprüche 1 bis 8, in welchem die tafelförmigen Körner mindestens 70 Molprozent Chlorid enthalten.
  10. Farbfotografisches Element nach Anspruch 9, in welchem die tafelförmigen Körner mindestens 90 Molprozent Chlorid enthalten.
  11. Farbfotografische Element nach irgendeinem der Ansprüche 1 bis 10, in welchem die tafelförmigen Körner Silberiodochloridkörner sind.
  12. Farbfotografisches Element nach irgendeinem der Ansprüche 1 bis 11, in welchem die fotografisch nützliche Gruppe ein Entwicklungsinhibitor ist.
  13. Farbfotografisches Element nach Anspruch 12, in welchem die Verbindung, die den Entwicklungsinhibitor enthält, ein Kuppler ist.
  14. Farbfotografisches Element nach Anspruch 12, in welchem der Entwicklungsinhibitor ein Mercaptotetrazol, Mercaptooxadiazol oder ein Mercaptothiadiazol ist.
  15. Farbfotografisches Element nach Anspruch 12, in welchem der Entwicklungsinhibitor ein Benzotriazol oder ein Tetrazol ist.
  16. Farbfotografisches Element nach irgendeinem der Ansprüche 1 bis 11, in welchem die fotografisch nützliche Gruppe ein Bleichbeschleuniger, Entwicklungsbeschleuniger, konkurrierender Kuppler, Elektronenübertragungsmittel, Bleichhemmer oder ein Farbstoff .ist.
  17. Farbfotografisches Element nach irgendeinem der Ansprüche 1 bis 11, in welchem das Entwicklungsmittel ein p-Phenylendiamin-Entwicklungsmittel ist.
  18. Farbfotografisches Element nach irgendeinem der Ansprüche 1 bis 17, in welchem die strahlungsempfindliche Emulsionssschicht blau-sensibilisiert ist.
  19. Farbfotografisches Element nach irgendeinem der Ansprüche 1 bis 17, welches mindestens eine rot-sensibilisierte Silberhalogenid-Emulsionsschicht, mindestens eine grün-sensibilisierte Silberhalogenid-Emulsionsschicht und mindestens eine blau-sensibilisierte Silberhalogenid-Emulsionsschicht umfaßt und in welchem mindestens eine dieser Emulsionsschichten die tafelförmigen Körner enthält, welche durch {100}-Hauptflächen begrenzt sind.
  20. Farbfotografisches Element nach Anspruch 19, in welchem mindestens eine der Silberhalogenid-Emulsionsschichten, die tafelförmige Silberhalogenidkörner enthält, welche durch {100}-Hauptflächen begrenzt sind, blau-sensibilisiert ist.
  21. Farbfotografisches Element nach Anspruch 19, in welchem mindestens eine der Silberhalogenid-Emulsionsschichten, die tafelförmige Silberhalogenidkörner enthält, welche durch {100}-Hauptflächen begrenzt sind, rot-sensibilisiert ist.
EP93907625A 1993-03-22 1993-03-22 Ein farbbild erzeugende photographische elemente Expired - Lifetime EP0641459B1 (de)

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PCT/US1993/002604 WO1994022054A1 (en) 1993-03-22 1993-03-22 Dye image forming photographic elements

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EP0641459A1 EP0641459A1 (de) 1995-03-08
EP0641459B1 true EP0641459B1 (de) 1999-08-11

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EP (1) EP0641459B1 (de)
JP (1) JP3333518B2 (de)
DE (1) DE69326000T2 (de)
WO (1) WO1994022054A1 (de)

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Publication number Priority date Publication date Assignee Title
US5665530A (en) * 1994-08-30 1997-09-09 Fuji Photo Film Co., Ltd. Silver halide emulsion and photographic material using the same
US5707793A (en) * 1995-04-19 1998-01-13 Fuji Photo Film Co., Ltd. Silver halide emulsion and silver halide photographic material using the same
US6228565B1 (en) 1996-10-28 2001-05-08 Fuji Photo Film Co., Ltd. Silver halide color photographic photosensitive material
US6051359A (en) * 1996-11-25 2000-04-18 Fuji Photo Film Co., Ltd. Heat developable light-sensitive material and method of forming color images

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GB1507989A (en) * 1974-12-19 1978-04-19 Ciba Geigy Ag Photographic emulsions
EP0369424B1 (de) * 1988-11-15 1995-09-27 Fuji Photo Film Co., Ltd. Lichtempfindliches photographisches Silberhalogenidmaterial
WO1993006521A1 (en) * 1991-09-24 1993-04-01 Eastman Kodak Company High tabularity high chloride emulsions of exceptional stability
US5176992A (en) * 1992-01-13 1993-01-05 Eastman Kodak Company Process for the preparation of a grain stabilized high chloride tabular grain photographic emulsion (II)

Also Published As

Publication number Publication date
DE69326000T2 (de) 2000-02-17
JPH07507645A (ja) 1995-08-24
JP3333518B2 (ja) 2002-10-15
DE69326000D1 (de) 1999-09-16
WO1994022054A1 (en) 1994-09-29
EP0641459A1 (de) 1995-03-08

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