EP1094363B1 - Elément photographique ayant un excellent différentiel de sensibilité pour des dispositifs d'exposition digitaux et optiques - Google Patents

Elément photographique ayant un excellent différentiel de sensibilité pour des dispositifs d'exposition digitaux et optiques Download PDF

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EP1094363B1
EP1094363B1 EP00203506A EP00203506A EP1094363B1 EP 1094363 B1 EP1094363 B1 EP 1094363B1 EP 00203506 A EP00203506 A EP 00203506A EP 00203506 A EP00203506 A EP 00203506A EP 1094363 B1 EP1094363 B1 EP 1094363B1
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Prior art keywords
dye
ligands
formula
emulsion
substituted
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EP1094363A2 (fr
EP1094363A3 (fr
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Pamela Mccue C/O Eastman Kodak Company Ferguson
Donald Richard C/O Eastman Kodak Company Diehl
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs therefor
    • G03C1/832—Methine or 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/127—Methine and polymethine dyes the polymethine chain forming part of a carbocyclic ring
    • 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
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/093—Iridium

Definitions

  • This invention relates to a photographic element which may be exposed by either optical and digital exposure devices.
  • a latent image is formed by the exposure of a silver halide emulsion which has been spectrally sensitized to a particular wavelength region of light by a suitable exposure device.
  • Such exposure devices may have a broad spectrum of light exposure ranging from wavelengths below 400 nanometers (nm) to above 700 nm for devices which are now in the trade as optical exposure devices, or the exposure devices may have a very narrow wavelength of exposure and such devices are known in the art as laser exposure devices.
  • the emulsion may be sensitized by a wide range of cyanine type spectral sensitizing dyes.
  • cyanine dyes are well known in the art and patents describing those types of dyes are set forth in Section V (A) of Research Disclosure, September 1996, Number 389, Item 38957, which will be identified hereafter by the term " Research Disclosure I.”
  • the Sections referred to herein are Sections of the Research Disclosure I unless otherwise indicated. All Research Disclosures referenced are published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire PO10 7DQ, ENGLAND.
  • the invention provides an imaging element comprising at least one silver halide emulsion wherein the silver halide emulsion grains incorporate:
  • the silver halide grains further comprise dopant (ii) which comprises an iridium coordination complex.
  • dopant (ii) contains a thiazole or substituted thiazole ligand.
  • the sensitizing dye is preferably selected from Dye A, Dye B and mixtures thereof, wherein Dye A is of formula I or II: wherein:
  • the filter dye preferably is of the formula: wherein:
  • the invention has numerous advantages over prior practices in the art.
  • the invention imaging elements provide the ability to have an imaging element that may be exposed with substantially invariant results over a wide range of exposure times.
  • the imaging element of the invention when digitally exposed at exposure times of about 125 nanoseconds produces a clear, bright, and sharp image while minimizing fringing or other undesirable artifacts.
  • the photographic element when digitally exposed maintains an acceptable maximum density in dark areas of the print, while also having the ability to print white whites in the white areas.
  • optical performance of the imaging element of the invention is exceptional with optical exposure resulting in bright, sharp prints. It is a feature of this invention that prints made either by optical or by digital exposure have substantially the same excellent characteristics.
  • a full color imaging element has at least one layer comprising a silver halide emulsion a cyan dye forming coupler and silver halide grains sensitized to red light, at least one layer comprising a silver halide emulsion a magenta dye forming coupler and silver halide grains sensitized to green light and at least one layer comprising a silver halide emulsion a yellow dye forming coupler and silver halide grains sensitized to blue light.
  • the emulsions can be spectrally sensitized with any of the dyes known to the photographic art, such as the polymethine dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines, oxonols, hemioxonols, styryls, merostyryls and streptocyanines.
  • the polymethine dye class which includes the cyanines, merocyanines, complex cyanines and merocyanines, oxonols, hemioxonols, styryls, merostyryls and streptocyanines.
  • Use of low staining sensitizing dyes in a photographic element processed in a developer solution with little or no optical brightening agent for instance, stilbene compounds such as Blankophor REUTM
  • these low staining dyes can be used in combination with other dyes known to the art ( Research Disclosure I, Section V).
  • Useful sensitizing dyes include, but are not limited to, the following.
  • the red sensitizing dye is selected from Dye A, Dye B and mixtures thereof, wherein Dye A is of formula I or II: wherein:
  • W 1 -W 8 preferably each independently represent an alkyl, acyl, acyloxy, alkoxycarbonyl, carbonyl, carbamoyl, sulfamoyl, carboxyl, cyano, hydroxy, amino, acylamino, alkoxy, alkylthio, alkylsulfonyl, sulfonic acid, aryl, or aryloxy group, any of which may be substituted or unsubstituted, or a hydrogen or halogen atom, and provided further that adjacent ones of W 1 -W 8 can be bonded to each other via their carbon atoms to form a condensed ring.
  • Dye A has structure I and substituents W 1 -W 8 are chosen such that J is ⁇ 0.0, or, alternatively, Dye A can also have the structure II provided substituents W 1 -W 8 are chosen such that J is ⁇ 0.24 and Dye B has structure II and substituents W 1 -W 8 are chosen such that J is ⁇ 0.10, or, alternatively, Dye B can also have structure I provided substituents W 1 -W 8 are chosen such that J is ⁇ - 0.14.
  • Hammett ⁇ p values are discussed in Advanced Organic Chemistry 3rd Ed., J. March, (John Wiley Sons, NY; 1985). Note that the " p " subscript refers to the fact that the ⁇ values are measured with the substituents in the para position.
  • Z is a hydrogen or halogen atom or an alkyl group or substituted alkyl group, for example a 1 to 8 carbon atom alkyl group or substituted alkyl group.
  • Z is a relatively "flat" substituent, such as a hydrogen, halogen or a methyl (substituted or unsubstituted). More particularly Z may be a substituted or unsubstituted methyl or a hydrogen.
  • Z 1 and Z 2 are independently a 1 to 8 carbon alkyl group (for example, methyl, ethyl, propyl, butyl).
  • R 1 or R 2 are alkyl of 1-8 carbon atoms, either of which alkyl may be substituted or unsubstituted.
  • substituents include acid or acid salt groups (for example, sulfo or carboxy groups).
  • R 1 or R 2 could be, for example, 2-sulfobutyl, 3-sulfopropyl, or sulfoethyl.
  • Dye A and Dye B used in materials of the present invention are listed below in Table A, but the present invention is not limited to the use of these dyes.
  • a silver halide photographic material comprises a red sensitive silver halide emulsion layer which has a dye of formula (Ia) used in combinations with a dye for formula (IIa): where:
  • Sensitizing dyes which are particularly valuable in red spectrally sensitized emulsions are shown below:
  • substituent group when reference in this application is made to a substituent "group”, this means that the substituent may itself be substituted or unsubstituted (for example "alkyl group” refers to a substituted or unsubstituted alkyl).
  • substituents on any “groups” referenced herein or where something is stated to be possibly substituted include the possibility of any groups, whether substituted or unsubstituted, which do not destroy properties necessary for the photographic utility. It will also be understood throughout this application that reference to a compound of a particular general formula includes those compounds of other more specific formula which specific formula falls within the general formula definition.
  • substituents on any of the mentioned groups can include known substituents, such as: halogen, for example, chloro, fluoro, bromo, iodo; alkoxy, particularly those with 1 to 6 carbon atoms (for example, methoxy, ethoxy); substituted or unsubstituted alkyl, particularly lower alkyl (for example, methyl, trifluoromethyl); alkenyl or thioalkyl (for example, methylthio or ethylthio), particularly either of those with 1 to 6 carbon atoms; substituted and unsubstituted aryl, particularly those having from 6 to 20 carbon atoms (for example, phenyl); and substituted or unsubstituted heteroaryl, particularly those having a 5 or 6-membered ring containing 1 to 3 heteroatoms selected from N, O, or S (for example, pyridyl, thienyl, furyl, pyrrolyl); and others known in the art.
  • Alkyl substituents may specifically include "lower alkyl", that is having from 1 to 6 carbon atoms, for example, methyl, ethyl. Further, with regard to any alkyl group, alkylene group or alkenyl group, it will be understood that these can be branched or unbranched and include ring structures.
  • Emulsions can be spectrally sensitized with mixtures of two or more sensitizing dyes which form mixed dye aggregates on the surface of the emulsion grain.
  • the use of mixed dye aggregates enables adjustment of the spectral sensitivity of the emulsion to any wavelength between the extremes of the wavelengths of peak sensitivities ( ⁇ -max) of the two or more dyes. This practice is especially valuable if the two or more sensitizing dyes absorb in similar portions of the spectrum (i.e., blue, or green or red and not green plus red or blue plus red or green plus blue).
  • the function of the spectral sensitizing dye is to modulate the information recorded in the negative which is recorded as an image dye, positioning the peak spectral sensitivity at or near the ⁇ -max of the image dye in the color negative produces the optimum preferred response.
  • the combination of similarly spectrally sensitized emulsions can be in one or more layers.
  • the filter dye preferably is of the formula: wherein:
  • Particularly preferred filter dyes are of the formula: wherein
  • the absorbance maximum and half band width of the dyes used in this invention in a photographic coating are shown in Table 2.
  • Absorbance maximum and half band width of filter dyes Dye Absorbance maximum (gelatin coating) Ratio of Absorbance Density O.D.( ⁇ max-50nm) /O.D.( ⁇ max)
  • Half Band Width Invention FD1 694 nm 0.58 95 nm Invention FD7 702 nm 0.60 100 nm Invention FD8 703 nm 0.65 100 nm Invention FD10 701 nm 0.59 96 nm Invention FD11 687 nm 0.64 100 nm Invention FD12 687 nm 0.62 100 nm Invention FD13 686 nm 0.63 98 nm Comparison CFD1 671 nm 0.59 100 nm Comparison CFD2 638 nm 0.60 102 nm Comparison CFD3 725 nm 0.71 192 nm Comparison CFD4
  • the silver halide contains dopant (i) which is a hexacoordination metal complex which satisfies the formula: [ML 6 ] n wherein
  • Any remaining ligands can be selected from among various other bridging ligands, including aquo ligands, halide ligands (specifically, fluoride, chloride, bromide and iodide), cyanate ligands, thiocyanate ligands, selenocyanate ligands, tellurocyanate ligands, and azide ligands. Hexacoordinated transition metal complexes of which include six cyano ligands are specifically preferred as dopant (i).
  • Dopant (i) is preferably introduced into the high chloride grains after at least 50 (most preferably 75 and optimally 80) percent of the silver has been precipitated, but before precipitation of the central portion of the grains has been completed.
  • dopant (i) is introduced before 98 (most preferably 95 and optimally 90) percent of the silver has been precipitated.
  • dopant (i) is preferably present in an interior shell region that surrounds at least 50 (most preferably 75 and optimally 80) percent of the silver and, with the more centrally located silver, accounts for the entire central portion (99 percent of the silver), most preferably accounts for 95 percent, and optimally accounts for 90 percent of the silver halide forming the high chloride grains.
  • Dopant (i) can be distributed throughout the interior shell region delimited above or can be added as one or more bands within the interior shell region.
  • Dopant (i) can be employed in any conventional useful concentration.
  • a preferred concentration range is from 10 -8 to 10 -3 mole per silver mole, most preferably from 10 -6 to 5 X 10 -4 mole per silver mole.
  • dopant (i) When dopant (i) have a net negative charge, it is appreciated that they are associated with a counter ion when added to the reaction vessel during precipitation.
  • the counter ion is of little importance, since it is ionically dissociated from the dopant in solution and is not incorporated within the grain.
  • Common counter ions known to be fully compatible with silver chloride precipitation, such as ammonium and alkali metal ions, are contemplated. It is noted that the same comments apply to Dopant (ii), otherwise described below.
  • the silver halide further comprises dopant (ii), which is an iridium coordination complex.
  • dopant (ii) is an iridium coordination complex.
  • iridium coordination complex containing at least one thiazole or substituted thiazole ligand.
  • Careful scientific investigations have revealed Group VIII hexahalo coordination complexes to create deep electron traps, as illustrated R. S. Eachus, R. E. Graves and M. T. Olm J . Chem. Phys ., Vol. 69, pp. 4580-7 (1978) and Physica Status Solidi A , Vol. 57, 429-37 (1980) and R. S. Eachus and M. T. Olm Annu . Rep . Prog . Chem. Sect. C.
  • Dopant (ii) employed in the practice of this invention are believed to create such deep electron traps.
  • the ligand can be any photographically acceptable ligand.
  • dopant (ii) contains a thiazole or substituted thiazole, wherein the substituent(s) can be any photographically acceptable substituent which does not prevent incorporation of dopant (ii) into the silver halide grains.
  • substituents include lower alkyl (e.g., alkyl groups containing 1-4 carbon atoms), and specifically methyl.
  • a specific example of a substituted thiazole ligand which may be used in accordance with the invention is 5-methylthiazole.
  • Dopant (ii) preferably is an iridium coordination complex having ligands each of which are more electropositive than a cyano ligand.
  • the remaining non-thiazole or non-substituted-thiazole ligands of the coordination complexes forming dopant (ii) are halide ligands.
  • Particularly preferred dopant (ii) contains a coordination complex containing organic ligands disclosed by Olm et al U.S. Patent 5,360,712, Olm et al U.S. Patent 5,457,021 and Kuromoto et al U.S. Patent 5,462,849.
  • Dopant (ii) is preferably introduced into the high chloride grains after at least 50 (most preferably 85 and optimally 90) percent of the silver has been precipitated, but before precipitation of the central portion of the grains has been completed.
  • dopant (ii) is introduced before 99 (most preferably 97 and optimally 95) percent of the silver has been precipitated.
  • dopant (ii) is preferably present in an interior shell region that surrounds at least 50 (most preferably 85 and optimally 90) percent of the silver and, with the more centrally located silver, accounts the entire central portion (99 percent of the silver), most preferably accounts for 97 percent, and optimally accounts for 95 percent of the silver halide forming the high chloride grains.
  • Dopant (ii) can be distributed throughout the interior shell region delimited above or can be added as one or more bands within the interior shell region.
  • Dopant (ii) can be employed in any conventional useful concentration.
  • a preferred concentration range is from 10 -9 to 10 -4 mole per silver mole.
  • Iridium is most preferably employed in a concentration range of from 10 -8 to 10 -5 mole per silver mole.
  • dopant (ii) is of the formula: (ii-1) [IrCl 5 (thiazole)] -2 (ii-2) [IrCl 4 (thiazole) 2 ] -1 (ii-3) [IrBr 5 (thiazole)] -2 (ii-4) [IrBr 4 (thiazole) 2 ] -1 (ii-5) [IrCl 5 (5-methylthiazole)] -2 (ii-6) [IrCl 4 (5-methylthiazole) 2 ] -1 (ii-7) [IrBr 5 (5-methylthiazole)] -2 or (ii-8) [IrBr 4 (5-methylthiazole) 2 ] -1
  • dopant is used in this application to mean a component that is added to a silver halide emulsion as it is precipitated such that the dopant is incorporated into the emulsion grains.
  • the silver halide grains preferably contain greater than 50 mole percent chloride, based on silver. Preferably the grains contain at least 70 mole percent chloride and, optimally at least 90 mole percent chloride, based on silver. Iodide can be present in the grains up to its solubility limit, which is in silver iodochloride grains, under typical conditions of precipitation, about 11 mole percent, based on silver. It is preferred for most photographic applications to limit iodide to less than 5 mole percent iodide, most preferably less than 2 mole percent iodide, based on silver.
  • silver bromide and silver chloride are miscible in all proportions. Hence, any portion, up to 50 mole percent, of the total halide not accounted for chloride and iodide, can be bromide.
  • bromide is typically limited to less than 10 mole percent based on silver and iodide is limited to less than 1 mole percent based on silver.
  • high chloride grains are precipitated to form cubic grains--that is, grains having ⁇ 100 ⁇ major faces and edges of equal length.
  • ripening effects usually round the edges and comers of the grains to some extent. However, except under extreme ripening conditions substantially more than 50 percent of total grain surface area is accounted for by ⁇ 100 ⁇ crystal faces.
  • High chloride tetradecahedral grains are a common variant of cubic grains. These grains contain 6 ⁇ 100 ⁇ crystal faces and 8 ⁇ 111 ⁇ crystal faces. Tetradecahedral grains are within the contemplation of this invention to the extent that greater than 50 percent of total surface area is accounted for by ⁇ 100 ⁇ crystal faces.
  • iodide is incorporated in overall concentrations of from 0.05 to 3.0 mole percent, based on silver, with the grains having a surface shell of greater than 50 ⁇ that is substantially free of iodide and a interior shell having a maximum iodide concentration that surrounds a core accounting for at least 50 percent of total silver.
  • Such grain structures are illustrated by Chen et al EPO 0 718 679.
  • the high chloride grains can take the form of tabular grains having ⁇ 100 ⁇ major faces.
  • Preferred high chloride ⁇ 100 ⁇ tabular grain emulsions are those in which the tabular grains account for at least 70 (most preferably at least 90) percent of total grain projected area.
  • Preferred high chloride ⁇ 100 ⁇ tabular grain emulsions have average aspect ratios of at least 5 (most preferably at least >8).
  • Tabular grains typically have thicknesses of less than 0.3 ⁇ m, preferably less than 0.2 ⁇ m, and optimally less than 0.07 ⁇ m.
  • High chloride ⁇ 100 ⁇ tabular grain emulsions and their preparation are disclosed by Maskasky U.S. Patents 5,264,337 and 5,292,632, House et al U.S. Patent 5,320,938, House et al U.S. Patent 5,314,798 and Chang et al U.S. Patent 5,413,904.
  • silver halide typically less than 1 percent, based on total silver, can be introduced to facilitate chemical sensitization. It is also recognized that silver halide can be epitaxially deposited at selected sites on a host grain to increase its sensitivity. For example, high chloride ⁇ 100 ⁇ tabular grains with comer epitaxy are illustrated by Maskasky U.S. Patent 5,275,930. For the purpose of providing a clear demarcation, the term "silver halide grain" is herein employed to include the silver necessary to form the grain up to the point that the final ⁇ 100 ⁇ crystal faces of the grain are formed.
  • Silver halide later deposited that does not overlie the ⁇ 100 ⁇ crystal faces previously formed accounting for at least 50 percent of the grain surface area is excluded in determining total silver forming the silver halide grains.
  • the silver forming selected site epitaxy is not part of the silver halide grains while silver halide that deposits and provides the final ⁇ 100 ⁇ crystal faces of the grains is included in the total silver forming the grains, even when it differs significantly in composition from the previously precipitated silver halide.
  • a imaging element contemplated for use in the electronic or optical printing method used in the invention can consist of a single emulsion layer satisfying the emulsion description provided above coated on a conventional photographic support, such as those described in Research Disclosure I, Section XVI.
  • the support is a white reflective support, such as photographic paper support or a film support that contains or bears a coating of a reflective pigment.
  • a white translucent support such as a DuratransTM or DuraclearTM support.
  • Image dye-forming couplers may be included in the element such as couplers that form cyan dyes upon reaction with oxidized color developing agents which are described in such representative patents and publications as: U.S. Patent Nos. 2,367,531; 2,423,730; 2,474,293; 2,772,162; 2,895,826; 3,002,836; 3,034,892; 3,041,236; 4,883,746 and "Farbkuppler - Eine Literatur Ubersicht,” published in Agfa Mitannonen, Band III, pp. 156-175 (1961).
  • couplers are phenols and naphthols that form cyan dyes on reaction with oxidized color developing agent.
  • an "NB coupler” is a dye-forming coupler which is capable of coupling with the developer 4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamidoethyl) aniline sesquisulfate hydrate to form a dye for which the left bandwidth (LBW) of its absorption spectra upon "spin coating" of a 3% w/v solution of the dye in di-n-butyl sebacate solvent is at least 5 nm. less than the LBW for a 3% w/v solution of the same dye in acetonitrile.
  • the LBW of the spectral curve for a dye is the distance between the left side of the spectral curve and the wavelength of maximum absorption measured at a density of half the maximum.
  • the "spin coating" sample is prepared by first preparing a solution of the dye in di-n-butyl sebacate solvent (3% w/v). If the dye is insoluble, dissolution is achieved by the addition of some methylene chloride. The solution is filtered and 0.1-0.2ml is applied to a clear polyethylene terephthalate support (approximately 4cm x 4cm) and spun at 4,000RPM using the Spin Coating equipment, Model No. EC101, available from Headway Research Inc., Garland TX. The transmission spectra of the so prepared dye samples are then recorded.
  • Preferred "NB couplers” form a dye which, in n-butyl sebacate, has a LBW of the absorption spectra upon "spin coating" which is at least 15 nm, preferably at least 25 nm, less than that of the same dye in a 3% solution (w/v) in acetonitrile.
  • cyan dye-forming "NB coupler” useful in the invention has the formula (NBC-1A) wherein
  • the coupler of formula (IA) is a 2,5-diamido phenolic cyan coupler wherein the substituents R' and R" are preferably independently selected from unsubstituted or substituted alkyl, aryl, amino, alkoxy and heterocyclyl groups.
  • the "NB coupler” has the formula (NBC-1): wherein
  • the coupler of formula (NBC-I) is a 2,5-diamido phenol in which the 5-amido moiety is an amide of a carboxylic acid which is substituted in the alpha position by a particular sulfone (-SO 2 -) group, such as, for example, described in U.S. Patent No. 5,686,235.
  • the sulfone moiety is an unsubstituted or substituted alkylsulfone or a heterocyclyl sulfone or it is an arylsulfone, which is preferably substituted, in particular in the meta and/or para position.
  • Couplers having these structures of formulae (NBC-I) or (NBC-IA) comprise cyan dye-forming "NB couplers" which form image dyes having very sharp-cutting dye hues on the short wavelength side of the absorption curves with absorption maxima ( ⁇ max ) which are shifted hypsochromically and are generally in the range of 620-645 nm, which is ideally suited for producing excellent color reproduction and high color saturation in color photographic papers.
  • R 17 and R 18 are independently hydrogen or an unsubstituted or substituted alkyl group, preferably having from 1 to 24 carbon atoms and in particular 1 to 10 carbon atoms, suitably a methyl, ethyl, n-propyl, isopropyl, butyl or decyl group or an alkyl group substituted with one or more fluoro, chloro or bromo atoms, such as a trifluoromethyl group.
  • R 17 and R 18 is a hydrogen atom and if only one of R 17 and R 18 is a hydrogen atom then the other is preferably an alkyl group having 1 to 4 carbon atoms, more preferably one to three carbon atoms and desirably two carbon atoms.
  • alkyl refers to an unsaturated or saturated straight or branched chain alkyl group, including alkenyl, and includes aralkyl and cyclic alkyl groups, including cycloalkenyl, having 3-8 carbon atoms and the term 'aryl' includes specifically fused aryl.
  • R 19 is suitably an unsubstituted or substituted amino, alkyl or aryl group or a 5-10 membered heterocyclic ring which contains one or more heteroatoms selected from nitrogen, oxygen and sulfur, which ring is unsubstituted or substituted, but is more suitably an unsubstituted or substituted phenyl group.
  • substituent groups for this aryl or heterocyclic ring include cyano, chloro, fluoro, bromo, iodo, alkyl- or aryl-carbonyl, alkyl- or aryl-oxycarbonyl, carbonamido, alkyl- or aryl-carbonamido, alkyl- or arylsulfonyl, alkyl- or aryl-sulfonyloxy, alkyl- or aryl-oxysulfonyl, alkyl- or arylsulfoxide, alkyl- or aryl-sulfamoyl, alkyl- or aryl-sulfonamido, aryl, alkyl, alkoxy, aryloxy, nitro, alkyl- or aryl-ureido and alkyl- or aryl-carbamoyl groups, any of which may be further substituted.
  • Preferred groups are halogen, cyano, alkoxycarbonyl, alkylsulfamoyl, alkyl-sulfonamido, alkylsulfonyl, carbamoyl, alkylcarbamoyl or alkylcarbonamido.
  • R 19 is a 4-chlorophenyl, 3,4-di-chlorophenyl, 3,4-difluorophenyl, 4-cyanophenyl, 3-chloro-4-cyanophenyl, pentafluorophenyl, or a 3- or 4-sulfonamidophenyl group.
  • R 20 when R 20 is alkyl it may be unsubstituted or substituted with a substituent such as halogen or alkoxy.
  • R''' when R''' is aryl or a heterocycle, it may be substituted. Desirably it is not substituted in the position alpha to the sulfonyl group.
  • R''' when R''' is a phenyl group, it may be substituted in the meta and/or para positions with one to three substituents independently selected from the group consisting of halogen, and unsubstituted or substituted alkyl, alkoxy, aryloxy, acyloxy, acylamino, alkyl- or aryl-sulfonyloxy, alkyl- or aryl-sulfamoyl, alkyl- or aryl-sulfamoylamino, alkyl- or aryl-sulfonamido, alkyl- or aryl-ureido, alkyl- or aryl-oxycarbonyl, alkyl- or aryl-oxy-carbonylamino and alkyl- or aryl-carbamoyl groups.
  • each substituent may be an alkyl group such as methyl, t-butyl, heptyl, dodecyl, pentadecyl, octadecyl or 1,1,2,2-tetramethylpropyl; an alkoxy group such as methoxy, t-butoxy, octyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy; an aryloxy group such as phenoxy, 4-t-butylphenoxy or 4-dodecyl-phenoxy; an alkyl- or aryl-acyloxy group such as acetoxy or dodecanoyloxy; an alkyl- or aryl-acylamino group such as acetamido, hexadecanamido or benzamido; an alkyl- or aryl-sulfonyloxy group such as methyl-sulf
  • the above substituent groups have 1 to 30 carbon atoms, more preferably 8 to 20 aliphatic carbon atoms.
  • a desirable substituent is an alkyl group of 12 to 18 aliphatic carbon atoms such as dodecyl, pentadecyl or octadecyl or an alkoxy group with 8 to 18 aliphatic carbon atoms such as dodecyloxy and hexadecyloxy or a halogen such as a meta or para chloro group, carboxy or sulfonamido. Any such groups may contain interrupting heteroatoms such as oxygen to form e.g. polyalkylene oxides.
  • Z is a hydrogen atom or a group which can be split off by the reaction of the coupler with an oxidized color developing agent, known in the photographic art as a 'coupling-off group' and may preferably be hydrogen, chloro, fluoro, substituted aryloxy or mercaptotetrazole, more preferably hydrogen or chloro.
  • Such groups determines the chemical equivalency of the coupler, i.e., whether it is a 2-equivalent or 4-equivalent coupler, and its particular identity can modify the reactivity of the coupler.
  • Such groups can advantageously affect the layer in which the coupler is coated, or other layers in the photographic recording material, by performing, after release from the coupler, functions such as dye formation, dye hue adjustment, development acceleration or inhibition, bleach acceleration or inhibition, electron transfer facilitation, color correction.
  • coupling-off groups include, for example, halogen, alkoxy, aryloxy, heterocyclyloxy, sulfonyloxy, acyloxy, acyl, heterocyclylsulfonamido, heterocyclylthio, benzothiazolyl, phosophonyloxy, alkylthio, arylthio, and arylazo.
  • These coupling-off groups are described in the art, for example, in U.S. Patent Nos. 2,455,169; 3,227,551; 3,432,521; 3,467,563; 3,617,291; 3,880,661; 4,052,212; and 4,134,766; and in U.K. Patent Nos. and published applications 1,466,728; 1,531,927; 1,533,039; 2,066,755A, and 2,017,704A. Halogen, alkoxy and aryloxy groups are most suitable.
  • the coupling-off group is a chlorine atom, hydrogen atom or p-methoxyphenoxy group.
  • the ballasting may be accomplished by providing hydrophobic substituent groups in one or more of the substituent groups.
  • a ballast group is an organic radical of such size and configuration as to confer on the coupler molecule sufficient bulk and aqueous insolubility as to render the coupler substantially nondiffusible from the layer in which it is coated in a photographic element.
  • the combination of substituent are suitably chosen to meet these criteria.
  • the ballast will usually contain at least 8 carbon atoms and typically contains 10 to 30 carbon atoms. Suitable ballasting may also be accomplished by providing a plurality of groups which in combination meet these criteria.
  • R 17 in formula (NBC-I) is a small alkyl group or hydrogen. Therefore, in these embodiments the ballast would be primarily located as part of the other groups. Furthermore, even if the coupling-off group Z contains a ballast it is often necessary to ballast the other substituents as well, since Z is eliminated from the molecule upon coupling; thus, the ballast is most advantageously provided as part of groups other than Z.
  • Preferred couplers are IC-3, IC-7, IC-35, and IC-36.
  • Couplers that form magenta dyes upon reaction with oxidized color developing agent are described in such representative patents and publications as: U.S. Patent Nos. 2,311,082, 2,343,703, 2,369,489, 2,600,788, 2,908,573, 3,062,653, 3,152,896, 3,519,429, 3,758,309, and "Farbkuppler-eine Literatur-Übersicht,” published in Agfa Mitannonen, Band III, pp. 126-156 (1961).
  • couplers are pyrazolones, pyrazolotriazoles, or pyrazolobenzimidazoles that form magenta dyes upon reaction with oxidized color developing agents.
  • Especially preferred couplers are 1H-pyrazolo [5,1-c]-1,2,4-triazole and 1H-pyrazolo [1,5-b]-1,2,4-triazole.
  • Examples of 1H-pyrazolo [5,1-c]-1,2,4-triazole couplers are described in U.K. Patent Nos. 1,247,493; 1,252,418; 1,398,979; U.S. Patent Nos. 4,443,536; 4,514,490; 4,540,654; 4,590,153; 4,665,015; 4,822,730; 4,945,034; 5,017,465; and 5,023,170.
  • 1H-pyrazolo [1,5-b]-1,2,4-triazoles can be found in European Patent applications 176,804; 177,765; U.S Patent Nos. 4,659,652; 5,066,575; and 5,250,400.
  • Couplers that form yellow dyes upon reaction with oxidized color developing agent are described in such representative patents and publications as: U.S. Patent Nos. 2,298,443; 2,407,210; 2,875,057; 3,048,194; 3,265,506; 3,447,928; 3,960,570; 4,022,620; 4,443,536; 4,910,126; and 5,340,703 and "Farbkuppler-eine Literaturschreibsicht,” published in Agfa Mitannonen, Band III, pp. 112-126 (1961).
  • Such couplers are typically open chain ketomethylene compounds.
  • yellow couplers such as described in, for example, European Patent Application Nos.
  • couplers which give yellow dyes that cut off sharply on the long wavelength side are particularly preferred (for example, see U.S. Patent No. 5,360,713).
  • Typical preferred yellow couplers are represented by the following formulas: wherein R 1 , R 2 , Q 1 and Q 2 each represents a substituent; X is hydrogen or a coupling-off group; Y represents an aryl group or a heterocyclic group; Q 3 represents an organic residue required to form a nitrogen-containing heterocyclic group together with the >N ⁇ ; and Q 4 represents nonmetallic atoms necessary to form a 3- to 5-membered hydrocarbon ring or a 3- to 5-membered heterocyclic ring which contains at least one hetero atom selected from N, O, S, and P in the ring. Particularly preferred is when Q 1 and Q 2 each represent an alkyl group, an aryl group, or a heterocyclic group, and R 2 represents an aryl or tertiary alkyl group.
  • Preferred yellow couplers can be of the following general structures
  • substituent groups which may be substituted on molecules herein include any groups, whether substituted or unsubstituted, which do not destroy properties necessary for photographic utility.
  • group When the term "group" is applied to the identification of a substituent containing a substitutable hydrogen, it is intended to encompass not only the substituent's unsubstituted form, but also its form further substituted with any group or groups as herein mentioned.
  • the group may be halogen or may be bonded to the remainder of the molecule by an atom of carbon, silicon, oxygen, nitrogen, phosphorous, or sulfur.
  • the substituent may be, for example, halogen, such as chlorine, bromine or fluorine; nitro; hydroxyl; cyano; carboxyl; or groups which may be further substituted, such as alkyl, including straight or branched chain alkyl, such as methyl, trifluoromethyl, ethyl, t -butyl, 3-(2,4-di-t-pentylphenoxy) propyl, and tetradecyl; alkenyl, such as ethylene, 2-butene; alkoxy, such as methoxy, ethoxy, propoxy, butoxy, 2-methoxyethoxy, sec -butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 2-(2,4-di- t -pentylphenoxy)ethoxy, and 2-dodecyloxyethoxy; aryl such as phenyl, 4-t-butylphenyl, 2,
  • substituents may themselves be further substituted one or more times with the described substituent groups.
  • the particular substituents used may be selected by those skilled in the art to attain the desired photographic properties for a specific application and can include, for example, hydrophobic groups, solubilizing groups, blocking groups, releasing or releasable groups, etc.
  • the above groups and substituents thereof may include those having up to 48 carbon atoms, typically 1 to 36 carbon atoms and usually less than 24 carbon atoms, but greater numbers are possible depending on the particular substituents selected.
  • ballast groups include alkyl, aryl, alkoxy, aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxcarbonyl, carboxy, acyl, acyloxy, amino, anilino, carbonamido, carbamoyl, alkylsulfonyl, arylsulfonyl, sulfonamido, and sulfamoyl groups wherein the substituents typically contain 1 to 42 carbon atoms. Such substituents can also be further substituted.
  • Stabilizers and scavengers that can be used in these photographic elements include, but are not limited to, the following.
  • solvents which may be used in the invention include the following: Tritolyl phosphate S-1 Dibutyl phthalate S-2 Diundecyl phthalate S-3 N , N -Diethyldodecanamide S-4 N , N -Dibutyldodecanamide S-5 Tris(2-ethylhexyl)phosphate S-6 Acetyl tributyl citrate S-7 2,4-Di-tert-pentylphenol S-8 2-(2-Butoxyethoxy)ethyl acetate S-9 1,4-Cyclohexyldimethylene bis(2-ethylhexanoate) S-10
  • the dispersions used in photographic elements may also include ultraviolet (UV) stabilizers and so called liquid UV stabilizers such as described in U.S. Patent Nos. 4,992,358; 4,975,360; and 4,587,346. Examples of UV stabilizers are shown below.
  • the aqueous phase may include surfactants.
  • Surfactant may be cationic, anionic, zwitterionic or non-ionic.
  • Useful surfactants include, but are not limited to, the following:
  • the photographic elements of this invention can be single color elements or multicolor elements.
  • Multicolor elements typically contain dye image-forming units sensitive to each of the three primary regions of the visible 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 silver halide emulsions employed in the elements of this invention can be either negative working or positive working. Suitable emulsions and their preparation are described in Research Disclosure I, Sections I and II and the publications cited therein. Suitable vehicles for the emulsion layers and other layers of elements of this invention are described in Research Disclosure I, Section IX and the publications cited therein.
  • the elements of the invention can include couplers as described in Research Disclosure I, Section VII, paragraphs D, E, F, and G and the publications cited therein. These couplers can be incorporated in the elements and emulsions as described in Research Disclosure I, Section VII, paragraph C and the publications cited therein.
  • the photographic elements of this invention or individual layers thereof can contain brighteners (see Research Disclosure I, Section V), antifoggants and stabilizers (see Research Disclosure I, Section VI), antistain agents and image dye stabilizers (see Research Disclosure I, Section VII, paragraphs I and J), light absorbing and scattering materials (see Research Disclosure I, Section VIII), hardeners, (see Research Disclosure I, Section IX), plasticizers and lubricants (see Research Disclosure I, Section XII), antistatic agents (see Research Disclosure I, XIII), matting agents (see Research Disclosure I, Section XVI) and development modifiers (see Research Disclosure I, Section XXI).
  • brighteners see Research Disclosure I, Section V
  • antifoggants and stabilizers see Research Disclosure I, Section VI
  • antistain agents and image dye stabilizers see Research Disclosure I, Section VII, paragraphs I and J
  • light absorbing and scattering materials see Research Disclosure I, Section VIII
  • hardeners see Research Disclosure I, Section IX
  • plasticizers and lubricants
  • the photographic elements can be coated on a variety of supports as described in Research Disclosure I, Section XVII and the references described therein.
  • the reflective support preferably includes a resin layer with a stabilizing amount of hindered amine extruded on the top side of the imaging layer substrate.
  • Hindered amine light stabilizers HALS
  • HALS Hindered amine light stabilizers
  • the hindered amine should be added to the polymer layer at 0.01- 5% by weight of said resin layer in order to provide resistance to polymer degradation upon exposure to UV light.
  • the preferred amount is at 0.05-3% by weight. This provides excellent polymer stability and resistance to cracking and yellowing while keeping the expense of the hindered amine to a minimum.
  • Examples of suitable hindered amines with molecular weights of less than 2300 are Bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate; Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate; Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)2-n-butyl-(3,5-di-tert-butyl-hydroxy-benzyl)malonate; 8-Acetyl-3-dodecyl-7,7,9,9-tetramethyl-1.3,8-triazaspiro(4,5)decane-2,4-dione; Tetra(2,2,6,6-tetramethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate; 1-(-2-[3,5-di-tert-butyl-4-hydroxyphenyl-propionyloxyl]ethyl)-4-(3,5-di-tert-
  • Suitable polymers for the resin layer include polyethylene, polypropylene, polymethylpentene, polystyrene, polybutylene, and mixtures thereof.
  • Polyolefin copolymers including copolymers of polyethylene, propylene and ethylene such as hexene, butene, and octene are also useful.
  • Polyethylene is most preferred, as it is low in cost and has desirable coating properties.
  • As polyethylene usable are high-density polyethylene, low-density polyethylene, linear low density polyethylene, and polyethylene blends.
  • suitable polymers include polyesters produced from aromatic, aliphatic or cycloaliphatic dicarboxylic acids of 4-20 carbon atoms and aliphatic or alicyclic glycols having from 2-24 carbon atoms.
  • suitable dicarboxylic acids include terephthalic, isophthalic, phthalic, naphthalene dicarboxylic acid, succinic, glutaric, adipic, azelaic, sebacic, fumaric, maleic, itaconic, 1,4-cyclohexanedicarboxylic, sodiosulfoisophthalic and mixtures thereof.
  • glycols examples include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, other polyethylene glycols and mixtures thereof.
  • Other polymers are matrix polyesters having repeat units from terephthalic acid or naphthalene dicarboxylic acid and at least one glycol selected from ethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol such as poly(ethylene terephthalate), which may be modified by small amounts of other monomers.
  • suitable polyesters include liquid crystal copolyesters formed by the inclusion of suitable amount of a co-acid component such as stilbene dicarboxylic acid.
  • suitable liquid crystal copolyesters are those disclosed in U.S. Patent Nos. 4,420,607; 4,459,402; and 4,468,510.
  • Useful polyamides include nylon 6, nylon 66, and mixtures thereof. Copolymers of polyamides are also suitable continuous phase polymers.
  • An example of a useful polycarbonate is bisphenol-A polycarbonate.
  • Cellulosic esters suitable for use as the continuous phase polymer of the composite sheets include cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, and mixtures or copolymers thereof.
  • Useful polyvinyl resins include polyvinyl chloride, poly(vinyl acetal), and mixtures thereof. Copolymers of vinyl resins can also be utilized.
  • any suitable white pigment may be incorporated in the polyolefin layer, such as, for example, zinc oxide, zinc sulfide, zirconium dioxide, white lead, lead sulfate, lead chloride, lead aluminate, lead phthalate, antimony trioxide, white bismuth, tin oxide, white manganese, white tungsten, and combinations thereof.
  • the preferred pigment is titanium dioxide because of its high refractive index, which gives excellent optical properties at a reasonable cost.
  • the pigment is used in any form that is conveniently dispersed within the polyolefin.
  • the preferred pigment is anatase titanium dioxide.
  • the most preferred pigment is rutile titanium dioxide because it has the highest refractive index at the lowest cost.
  • the average pigment diameter of the rutile TiO 2 is most preferably in the range of 0.1 to 0.26 ⁇ m.
  • the pigments that are greater than 0.26 ⁇ m are too yellow for an imaging element application and the pigments that are less than 0.1 ⁇ m are not sufficiently opaque when dispersed in polymers.
  • the white pigment should be employed in the range of from 10 to 50 percent by weight, based on the total weight of the polyolefin coating. Below 10 percent TiO 2 , the imaging system will not be sufficiently opaque and will have inferior optical properties. Above 50 percent TiO 2 , the polymer blend is not manufacturable.
  • the surface of the TiO 2 can be treated with an inorganic compounds such as aluminum hydroxide, alumina with a fluoride compound or fluoride ions, silica with a fluoride compound or fluoride ion, silicon hydroxide, silicon dioxide, boron oxide, boria-modified silica (as described in US Patent 4,781,761), phosphates, zinc oxide, ZrO 2 , etc. and with organic treatments such as polyhydric alcohol, polyhydric amine, metal soap, alkyl titanate, polysiloxanes, silanes.
  • the organic and inorganic TiO 2 treatments can be used alone or in any combination.
  • the amount of the surface treating agents is preferably in the range of 0.2 to 2.0% for the inorganic treatment and 0.1 to 1% for the organic treatment, relative to the weight of the weight of the titanium dioxide. At these levels of treatment the TiO 2 disperses well in the polymer and does not interfere with the manufacture of the imaging support.
  • the polymer, hindered amine light stabilizer, and the TiO 2 are mixed with each other in the presence of a dispersing agent.
  • dispersing agents are metal salts of higher fatty acids such as sodium palmitate, sodium stearate, calcium palmitate, sodium laurate, calcium stearate, aluminum stearate, magnesium stearate, zirconium octylate, zinc stearate, higher fatty acids, higher fatty amide, and higher fatty acids.
  • the preferred dispersing agent is sodium stearate and the most preferred dispersing agent is zinc stearate. Both of these dispersing agents give superior whiteness to the resin-coated layer.
  • the layers of the waterproof resin coating preferably contain colorants such as a bluing agent and magenta or red pigment.
  • Applicable bluing agents include commonly know ultramarine blue, cobalt blue, oxide cobalt phosphate, quinacridone pigments, and a mixture thereof.
  • Applicable red or magenta colorants are quinacridones and ultramarines.
  • the resin may also include a fluorescing agent, which absorb energy in the UV region and emit light largely in the blue region. Any of the optical brighteners referred to in U.S. Patent 3,260,715 or a combination thereof would be beneficial.
  • the resin may also contain an antioxidant(s) such as hindered phenol primary antioxidants used alone or in combination with secondary antioxidants.
  • hindered phenol primary antioxidants include pentaerythrityl tetrakis [3-(3,5-di- tert -butyl-4-hydroxyphenyl)proprionate] (such as Irganox 1010), octadecyl 3-(3,5-di- tert -butyl-4-hydroxyphenyl)proprionate (such as Irganox 1076 which will be referred to as compound B), benzenepropanoic acid 3,5-bis(1,1-dimethyl)-4-hydroxy-2[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)-1-oxopropyl)hydrazide (such as Irganox MD1024), 2,2'-thiodiethylenebis[3-(3,5-di- tert -butyl
  • Secondary antioxidants include organic alkyl and aryl phosphites including examples such as triphenylphosphite (such as Irgastab TPP), tri(n-propylphenyl-phophite) (such as Irgastab SN-55), 2,4-bis(1,1-dimethylphenyl) phosphite (such as Irgafos 168).
  • triphenylphosphite such as Irgastab TPP
  • tri(n-propylphenyl-phophite) such as Irgastab SN-55
  • 2,4-bis(1,1-dimethylphenyl) phosphite such as Irgafos 168.
  • the hindered amine light stabilizer, TiO 2 , colorants, slip agents, optical brightener, and antioxidant are incorporated either together or separately with the polymer using a continuous or Banburry mixer.
  • a concentrate of the additives in the form of a pellet is typically made.
  • the concentration of the rutile pigment can be from 20% to 80% by weight of the masterbatch. The master batch is then adequately diluted for use with the resin.
  • the support to which the waterproof resin layer is laminated may be a polymeric, a synthetic paper, cloth, woven polymer fibers, or a cellulose fiber paper support, or laminates thereof.
  • the base also may be a microvoided polyethylene terephthalate such as disclosed in U.S. Patent Nos. 4,912,333; 4,994,312; and 5,055,371.
  • the preferred support is a photographic grade cellulose fiber paper.
  • the pellet containing the pigment and other additives is subjected to hotmelt coating onto a running support of paper or synthetic paper. If desired, the pellet is diluted with a polymer prior to hot melt coating.
  • the resin layer may be formed by lamination.
  • the die is not limited to any specific type and may be any one of the common dies such as a T-slot or coat hanger die.
  • An exit orifice temperature in heat melt extrusion of the water-proof resin ranges from 260-349°C (500-660°F).
  • the support may be treated with an activating treatment such as corona discharge, flame, ozone, plasma, or glow discharge.
  • the resin layer is a biaxially oriented polyolefin sheet as described in U.S. Patent No. 5,853,965 or a microvoided biaxially oriented polyolefin sheet as described in U.S. Patent No. 5,866,282.
  • the thickness of the resin layer which is applied to a base paper of the reflective support used in the present invention at a side for imaging is preferably in the range of 5 to 100 ⁇ m and most preferably in the range of 10 to 50 ⁇ m.
  • the thickness of the resin layer applied to a base paper on the side opposite the imaging element is preferably in a range from 5 to 100 ⁇ m and more preferably from 10 to 50 ⁇ m.
  • the surface of the waterproof resin coating at the imaging side may be a glossy, fine, silk, grain, or matte surface.
  • On the surface of the water-proof coating on the backside which is not coated with an imaging element may also be glossy, fine, silk, or matte surface.
  • the preferred water-proof surface for the backside away from the imaging element is matte.
  • the invention employs imaging elements which are constructed to contain at least three silver halide emulsion layer units.
  • a suitable full color, multilayer format for a imaging element used in the invention is represented by Structure I. wherein the red-sensitized, cyan dye image-forming silver halide emulsion unit is situated nearest the support; next in order is the green-sensitized, magenta dye image-forming unit, followed by the uppermost blue-sensitized, yellow dye image-forming unit.
  • the image-forming units are separated from each other by hydrophilic colloid interlayers containing an oxidized developing agent scavenger to prevent color contamination.
  • Silver halide emulsions satisfying the grain and gelatino-peptizer requirements described above can be present in any one or combination of the emulsion layer units.
  • Additional useful multicolor, multilayer formats for an element of the invention include structures as described in U.S. Patent 5,783,373. Each of such structures in accordance with the invention preferably would contain at least three silver halide emulsions comprised of high chloride grains having at least 50 percent of their surface area bounded by ⁇ 100 ⁇ crystal faces and containing dopants from classes (i) and (ii), as described above.
  • each of the emulsion layer units contains emulsion satisfying these criteria.
  • the invention employs imaging elements which are constructed as described in U.S. Patent No. 5,948,601.
  • the invention employs imaging elements which are constructed to contain at least three silver halide emulsion layer units and an interlayer adjacent to the blue sensitive emulsion layer
  • the imaging element of the invention comprises a multilayer full color imaging element have at least one layer comprising a silver halide emulsion a cyan dye forming coupler and silver halide grains sensitized to red light, at least one layer comprising a silver halide emulsion a magenta dye forming coupler and silver halide grains sensitized to green light and at least one layer comprising a silver halide emulsion a yellow dye forming coupler and silver halide grains sensitized to blue light.
  • Coupler dispersions were emulsified by methods well known to the art and the following layers were coated on the following support:
  • the following light sensitive silver halide imaging layers were utilized to prepare photographic print materials for the invention.
  • the following imaging layers were coated utilizing curtain coating.
  • Layer Item Laydown (g/m 2 ) Layer 1 Blue Sensitive Layer Gelatin 1.3127 Blue sensitive silver (Blue EM-1) 0.2399 Y-1 0.4143 ST-23 0.4842 Tributyl Citrate 0.2179 ST-24 0.1211 ST-16 0.0095 Sodium Phenylmercaptotetrazole 0.0001 Piperidino hexose reductone 0.0024 5-chloro-2-methyl-4-isothiazolin-3-one/2-methyl-4-isothiazolin-3-one(3/1) 0.0002 SF-1 0.0366 Potassium chloride 0.0204 Dye-1 0.0148 Layer 2 Interlayer Gelatin 0.7532 ST-4 0.1076 S-3 0.1969 5-chloro-2-methyl-4-isothiazolin-3-one/2-methyl-4-isothiazolin-3-one(3/1) 0.0001 Catechol
  • the following light sensitive silver halide imaging layers can be coated on a support to form an imaging element.
  • Item Laydown g/m 2 Layer 1 Blue Sensitive Layer Gelatin 1.3885 Blue Sensitive silver (Blue EM-1a) ] 0.2799 Y-5 0.4521 ST-6 0.0775 ST-7 0.0258 S-3 0.1981 Piperidino hexose reductone 0.0023 Sodium phenylinercaptotetrazole 0.0001 DYE-1 0.0323 Layer 2 Split Yellow Interlayer Gelatin 0.3229 Y-5 0.1938 ST-6 0.0332 ST-7 0.0111 S-3 0.0849 Layer 3 Interlayer Gelatin 0.7535 ST-4 0.0660 S-2 0.1884 Acrylamide/t-Butylacrylamide sulfonate copolymer 0.1281 Bis-vinylsulfonylmethane 0.0151 Layer 4 Green Sensitive Layer Gelatin 1.3498 Green Sensitive silver (Green EM-1a) ] 0.1076 M-1 0.2142 S
  • the multilayer imaging element has the following exposure characteristics : an exposure range of between 1000 nanoseconds and 0.5 seconds when there is a density loss of no more than 10 percent as a function of the red shoulder color record, wherein said photographic element has an exposure range of between 1000 nanoseconds and 0.5 seconds when there is a density loss of no more than 8 percent as a function of the green shoulder color record, wherein said photographic element has an exposure range of between 1000 nanoseconds and 0.5 seconds when there is a density loss of no more than 5 percent as a function of the blue shoulder color record, wherein said photographic element has an exposure range of between 1000 nanoseconds and 0.5 seconds when there is a density loss of no more than 6 percent as a function of the red Dmax color record, wherein said photographic element has an exposure range of between 1000 nanoseconds and 0.5 seconds when there is a density loss of no more than 9 percent as a function of the green Dmax color record, wherein said photographic element has an exposure range of between 1000 nanoseconds and 0.5 seconds when there is a density loss of no more than 10
  • the imaging elements comprising the radiation sensitive high chloride emulsion layers according to this invention can be conventionally optically printed, or in accordance with a particular embodiment of the invention can be image-wise exposed in a pixel-by-pixel mode using suitable high energy radiation sources typically employed in electronic printing methods.
  • suitable actinic forms of energy encompass the ultraviolet, visible and infrared regions of the electromagnetic spectrum as well as electron-beam radiation and is conveniently supplied by beams from one or more light emitting diodes or lasers, including gaseous or solid state lasers. Exposures can be monochromatic, orthochromatic or panchromatic.
  • exposure can be provided by laser or light emitting diode beams of appropriate spectral radiation, for example, infrared, red, green or blue wavelengths, to which such element is sensitive.
  • Multicolor elements can be employed which produce cyan, magenta and yellow dyes as a function of exposure in separate portions of the electromagnetic spectrum, including at least two portions of the infrared region, as disclosed in the previously mentioned U.S. Patent No. 4,619,892.
  • Suitable exposures include those up to 2000 nm, preferably up to 1500 nm.
  • Suitable light emitting diodes and commercially available laser sources are known and commercially available.
  • Imagewise exposures at ambient, elevated or reduced temperatures and/or pressures can be employed within the useful response range of the imaging element determined by conventional sensitometric techniques, as illustrated by T.H. James, The Theory of the Photographic Process , 4th Ed., Macmillan, 1977, Chapters 4, 6, 17, 18 and 23.
  • the quantity or level of high energy actinic radiation provided to the recording medium by the exposure source is generally at least 10 -4 ergs/cm 2 , typically in.the range of about 10 -4 ergs/cm 2 to 10 -3 ergs/cm 2 and often from 10 -3 ergs/cm 2 to 10 2 ergs/cm 2 .
  • Exposure of the recording element in a pixel-by-pixel mode as known in the prior art persists for only a very short duration or time. Typical maximum exposure times are up to 100 ⁇ seconds, often up to 10 ⁇ seconds, and frequently up to only 0.5 ⁇ seconds. Single or multiple exposures of each pixel are contemplated.
  • pixel density is subject to wide variation, as is obvious to those skilled in the art. The higher the pixel density, the sharper the images can be, but at the expense of equipment complexity. In general, pixel densities used in conventional electronic printing methods of the type described herein do not exceed 10 7 pixels/cm 2 and are typically in the range of about 10 4 to 10 6 pixels/cm 2 .
  • An assessment of the technology of high-quality, continuous-tone, color electronic printing using silver halide photographic paper which discusses various features and components of the system, including exposure source, exposure time, exposure level and pixel density and other recording element characteristics is provided in Firth et al., A Continuous-Tone Laser Color Printer , Journal of Imaging Technology, Vol. 14, No. 3, June 1988.
  • the imaging element can be processed as described in Research Disclosure I, Section XVIII, and then processed to form a visible dye image as described in Research Disclosure I, Section XIX.
  • Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. Oxidized color developing agent in turn reacts with the coupler to yield a dye.
  • the processing step described above gives a negative image.
  • this step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and then uniformly fogging the element to render unexposed silver halide developable.
  • a direct positive emulsion can be employed to obtain a positive image.
  • the photographic elements were prepared as follows:
  • Blue EM-1b Blue Sensitive Emulsion
  • a high chloride silver halide emulsion was precipitated by adding approximately equimolar silver nitrate and sodium chloride solutions into a reactor vessel containing a gelatin peptizer and a thioether ripener.
  • Cesium pentachloronitrosylosmate(II) dopant was added during the silver halide grain formation for most of the precipitation followed by addition of potassium hexacyanoruthenate(II), a small amount of KI solution and shelling without any dopant.
  • the resultant emulsion contained cubic shaped grains of 0.64 ⁇ m in edge length size.
  • the emulsion was optimally sensitized by the addition of a colloidal suspension of aurous sulfide followed by a heat ramp, and addition of blue sensitizing dye, BSD-1, 1-(3-acetamidophenyl)-5-mercaptotetrazole, an optimal amount of glutaryldiaminophenyl disulfide and Lippmann bromide, iridium hexachloroiridate.
  • Green EM-1b green sensitive emulsion
  • a high chloride silver halide emulsion was precipitated by adding approximately equimolar silver nitrate and sodium chloride solutions into a reactor vessel containing a gelatin peptizer and a thioether ripener.
  • Cesium pentachloronitrosyl osmate(II) dopant was added during the silver halide grain formation for most of the precipitation followed by shelling without dopant.
  • the resultant emulsion contained cubic shaped grains of 0.34 ⁇ m in edge length size.
  • the emulsion was optimally sensitized by the addition of a colloidal suspension of aurous sulfide followed by a heat ramp, and addition of an iridium dopant, Lippmann bromide and 1-(3-acetamidophenyl)-5-mercaptotetrazole, green sensitizing dye, GSD-2, and further 1-(3-acetamidophenyl)-5-mercaptotetrazole.
  • red sensitive emulsion (Red EM-1b).
  • a high chloride silver halide emulsion was precipitated by adding approximately equimolar silver nitrate and sodium chloride solutions into a reactor vessel containing a gelatin peptizer and a thioether ripener.
  • the resultant emulsion contained cubic shaped grains of 0.38 ⁇ m in edge length size.
  • the emulsion was optimally sensitized by the addition of a colloidal suspension of aurous sulfide followed by a heat ramp, and addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole, potassium bromide and red sensitizing dye, RSD1.
  • iridium and ruthenium doctors were added during the sensitization process.
  • Red sensitive emulsion Preparation of red sensitive emulsion (Red EM-2).
  • a high chloride silver halide emulsion was precipitated by adding approximately equimolar silver nitrate and sodium chloride solutions into a reactor vessel containing a gelatin peptizer and a thioether ripener.
  • the resultant emulsion contained cubic shaped grains of 0.38 ⁇ m in edge length size.
  • the emulsion was optimally sensitized by the addition of a solution of sensitizer Z' followed by a heat ramp, and addition of 1-(3-acetamidophenyl)-5-mercaptotetrazole, potassium bromide and red sensitizing dye, RSD1.
  • iridium and ruthenium dopants were added during the precipitation process.
  • Red sensitive emulsion (Red EM-3) An AgClBr cubic grain emulsion, 0.60%Br, 0.21 micron, spectrally sensitized with SD-2, 0,043mmole/Ag mole, laid down at 68.9 mg/sq.m.
  • the red sensitive emulsion was combined with dispersion using techniques known in the art and the resulting light-sensitive silver halide components were applied to polyethylene resin coated paper support as described in COATING FORMAT 1 to provide Examples 1-4.
  • the amount of absorber dye filter dyes FD 1-13 in Examples 1-5 was adjusted to give approximately equal speed attenuation as the comparison dyes.
  • Example 5 the red, blue and green sensitive emulsions were combined with dispersions using techniques known in the art and the resulting light-sensitive silver halide components were applied to polyethylene resin coated paper support to give a multilayer coating COATING FORMAT 2: COATING FORMAT 1 Layer 1 g/m 2 Gelatin 1.198 Silver (Red EM-1b, or EM-3) 0.19 C-1 0.365 S-1 0.358 UV-2 0.235 S-3 0.03 D-6 0.02 Layer 2 Gelatin 0.697 Surfactant 0.04 Lubricant 0.027 COATING FORMAT 2 Layer 1 g/m 2 Gelatin 1.321 Silver (Blue EM-1b) 0.203 Y1 0.418 S-1 0.285 ST-1 1.393 D-4 0.008 Layer 2 Gelatin 0.65 scavenger 0.057 S-1 0.163 Layer 3 Gelatin 1.087 Silver (Green EM-1b) 0.172 M-1 0.365 S-2 0.635 S-3 0.059 ST-2 0.404 scavenger 0.037 D-5 0.006 Layer 4 Gelatin
  • the samples were exposed through a step wedge and processed using conventional processing solutions and conditions.
  • the processed color photographic paper strips were measured for spectral sensitivity maximum ( ⁇ max), density at wavelength of sensitivity maximum (Speed1) and density at wavelength of sensitivity [maximum - 50 nm] (Speed2).
  • ⁇ max spectral sensitivity maximum
  • Speed1 density at wavelength of sensitivity maximum
  • Speed2 density at wavelength of sensitivity [maximum - 50 nm]
  • the percent ratio of Speed2/Speed1 is shown as DIFSP and represents the differential speed between an optical exposure device and a digital exposure device operating with a 50 nm shorter exposing wavelength maximum.
  • the data are shown in Tables 3-7.
  • a coated element was prepared to examine the effect of filter dyes with absorbance maximum greater than 15 nm different than the spectral sensitization maximum upon the differential speed factor DIFSP.
  • the red emulsion used was Red EM-Ib.
  • a coated element was prepared to examine the effect of minor variations in the structure of the filter dyes upon the differential speed factor DIFSP.
  • the red emulsion used was Red EM-1b.
  • Element Filter Dye Filter Dye ⁇ max Spec Sens ⁇ max Speed1 Speed2 DIFSP 201 Comparison CFD1 671nm 710nm 153 95 62.1% 202 for Invention FD7 702nm 700nm 160 110 68.7% 203 for Invention FD8 703nm 700nm 153 108 70.6% 204 for Invention FD10 701nm 700nm 154 110 71.9% 205 for Invention FD11 687nm 700nm 145 98 67.6% 206 for Invention FD12 687nm 700nm 145 95 65.5% 207 for Invention FD13 686nm 700nm 150 100 66.6%
  • a coated element was prepared to examine the effect of different substitution in the polymethine chain of the filter dyes upon the differential speed factor DIFSP.
  • the red emulsion used was Red EM-1b Element Filter Dye Filter Dye ⁇ max Spec Sens ⁇ max Speed1 Speed2 DIFSP 301 Comparison CFD1 671nm 710nm 163 105 64.4% 302 for Invention FD1 694nm 700nm 146 106 72.6% 303 for Invention FD8 703nm 700nm 151 112 74.1%
  • Table 5 shows for FD1 which has a chain methyl substituent that the structure of the substituent on the pentamethine chain of the dyes used in the invention may be changed to provide dyes with an absorbance maximum nearly identical with the spectral sensitization maximum and, therefore, excellent short red speed suitable for use with both optical and digital exposure devices.
  • a coated element was prepared to examine the effect of the half band width of the filter dyes upon the differential speed factor (DIFSP).
  • DIFSP differential speed factor
  • the red emulsion used was Red EM-3 Element Filter Dye Filter Dye ⁇ max Spec Sens ⁇ max Speed1 Speed2 DIFSP 401 Comparison CFD3 725nm 700nm 250 150 60% 402 for Invention FD13 686nm 700nm 250 175 70%
  • Comparison Filter Dye 3 which has an absorbance maximum near the spectral sensitization maximum but has a broad half band width, see Table 2, does not provide good short red speed and would not provide a method of manufacturing a photographic element suitable for use in both a optical and digital exposure device.
  • a coated element was prepared to examine the effect of the invention dye in a full multilayer embodiment where all three color records plus typical interlayers and overcoats are included.
  • the green emulsion used was green EM-1b
  • the blue emulsion used was blue EM 1b
  • the red emulsion used was Red EM-2.

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Claims (10)

  1. Elément formateur d'image comprenant au moins une émulsion aux halogénures d'argent, dans lequel les grains de l'émulsion aux halogénures d'argent incorporent un dopant (i) qui comprend un complexe métallique d'hexacoordination répondant à la formule : [ML6]n dans laquelle n est égal à zéro, -1, -2, -3 ou -4 ; M est un ion métallique polyvalent à orbitale frontière occupée, autre que l'iridium ; et L6 représente des ligands de pontage qui peuvent être choisis séparément, à condition que au moins quatre des ligands soient des ligands anioniques et au moins un des ligands soit un ligand cyano ou un ligand plus électronégatif qu'un ligand cyano ;
       et dans lequel l'émulsion a été sensibilisée spectralement par un colorant sensibilisateur et contient un colorant-filtre qui
    (a) a une longueur d'onde d'absorption maximale qui diffère de moins de 15 nm de la longueur d'onde maximale de sensibilité de l'émulsion conférée par le colorant sensibilisateur spectral, et
    (b) a une largeur de bande à mi-hauteur qui est égale à la largeur de bande à mi-hauteur du colorant sensibilisateur,
       pour obtenir ainsi une émulsion qui a une sensibilité à une longueur d'onde inférieure de 50 nm à la longueur d'onde maximale de sensibilisation qui est égale à au moins 65 % de la sensibilité de l'émulsion à la longueur d'onde maximale de sensibilité spectrale.
  2. Elément formateur d'image selon la revendication 1, dans lequel le colorant sensibilisateur est choisi parmi le colorant A et le colorant B, ou des mélanges de ceux-ci,
       dans lequel le colorant A répond à la formule I ou II :
    Figure 00890001
    Figure 00900001
    dans lesquelles :
    dans la formule I, les substituants W1-W8 sont choisis de telle sorte que J est supérieur ou égal à 0,0, J étant définicomme la somme des valeurs σp de Hammet de W1-W8, ou dans la formule II, les substituants W1-W8 sont choisis de telle sorte que J est supérieur ou égal à 0,24 ;
    R1 et R2 représentent chacun séparément un groupe alkyle ou un groupe alkyle substitué ;
    Z1 et Z2 représentent chacun séparément un groupe alkyle contenant 1 à 8 atomes de carbone ;
    X représente un contre-ion évertuellement nécessaire pour équilibrer la charge du colorant ;
       et dans lequel le colorant B répond à la formule I ou II, dans lesquelles :
    dans la formule I, les substituants W1-W8 sont choisis de telle sorte que J est inférieur à 0,10, ou dans la formule II, les substituants W1-W8 sont choisis de telle sorte que J est inférieur à -0, 14 ;
    R1 et R2 représentent chacun séparément un groupe alkyle ou un groupe alkyle substitué ;
    X représente un contre-ion éventuellement nécessaire pour équilibrer la charge du colorant ;
    Z représente un atome d'hydrogène ou d'halogène, un groupe alkyle ou un groupe alkyle substitué.
  3. Elément formateur d'image selon la revendication 1, dans lequel le colorant sensibilisateur est un colorant de formule (Ia) et/ou un colorant de formule (IIa) :
    Figure 00910001
    Figure 00910002
       dans lesquelles :
    R1 et R2 représentent chacun séparément un groupe alkyle ou un groupe alkyle substitué ;
    V2-V7 représentent séparément H ou un groupe alkyle contenant 1 à 8 atomes de carbone ;
    Z représente un atome d'hydrogène ou un groupe méthyle ;
    A représente un contre-ion éventuellement nécessaire pour équilibrer la charge.
  4. Elément formateur d'image selon l'une quelconque des revendications précédentes,dans lequel le colorant-filtre répond à la formule :
    Figure 00910003
    dans laquelle :
    G et G' représentent séparément un atome d'oxygène, un atome d'azote substitué ou C(CN)2 ;
    R3, R3', R4 et R4' représentent séparément Hou un substituant, ou R3 et R4, R3' et R4' peuvent former un noyau ;
    R5 représente un groupe acyle, alcoxycarbonyle, amido, carbamoyle, alkyle, aryle ou alkyloxy, pouvant chacun être substitué ou non substitué ;
    m est égal à 0, 1, 2 ou 3 ;
    l'ensemble des groupes L" définit une chaíne méthinique, chaque groupe L" représentart un groupe méthirique qui peut être substitué ou non substitué ; et
    M+ est un cation ou un proton.
  5. Elément formateurd'image selon la revendication 4, dans lequel le colorant-filtre répond à la formule :
    Figure 00920001
       dans laquelle :
    R5 et R6 représentent chacun séparément H ou un substituant, ou R5 et R6 peuvent former un noyau ;
    R7 représente un groupe acyle, alcoxycarbonyle, amido, carbamoyle, alkyle, aryle, alcoxy, aryloxy, amino ou hérérocyclique, pouvant chacun être substitué ou non substitué ; et
    M+ est un cation ou un proton.
  6. Elément formateurd'image selon la revendication 5, dans lequel le colorant-filtre est un colorant de formule :
    Figure 00920002
    dans laquelle M+ est un cation.
  7. Elément formateur d'image selon l'une quelconque des revendications précédentes, dans lequel L6 représente des ligands de pontage qui peuvent être choisis séparément, à condition que au moins quatre des ligands soient des ligands anioniques, et au moins un des ligands soit un ligand cyano ou un ligand plus électronégatif qu'un ligand cyano ; et les autres ligands sont choisis parmi les ligands aquo, les ligands halogénures, les ligands cyanates, les ligands thiocyanates, les ligands sélénocyanates, les ligands tellurocyanates et les ligands azides.
  8. Elément formateur d' image selon la revendication 7, dans lequel chaque L6 est un ligand cyano.
  9. Elément formateur d'image selon l'une quelconque des revendications précédentes, qui comprend aussi un dopant (ii) qui est un complexe d'iridium.
  10. Elément formateur d'image selon la revendication 9, dans lequel le dopant (ii) comprend un complexe d'hexacoordination répondant à la formule : [IrL1 6]n' dans laquelle :
    n'est égal à zéro, -1, -2, -3 ou -4 ; et
    L1 6 représente six ligands de pontage qui peuvent être choisis séparément, à condition que au moins quatre des ligands soient des ligands anioniques, chacun des ligands étant plus électropositif qu'un ligand cyano.
EP00203506A 1999-10-20 2000-10-10 Elément photographique ayant un excellent différentiel de sensibilité pour des dispositifs d'exposition digitaux et optiques Expired - Lifetime EP1094363B1 (fr)

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