Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
  • G03C1/498—Photothermographic systems, e.g. dry silver
  • G03C1/49836—Additives
  • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
• • 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
  • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
  • G03C1/498—Photothermographic systems, e.g. dry silver
• • 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
  • G03C2001/03535—Core-shell 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
  • G03C1/06—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
  • G03C2001/091—Gold
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/167—X-ray

Definitions

• This invention relates to photothermographic materials containing silver halides that have been chemically sensitized using certain combinations of gold(III)-containing compounds and diphenylphosphine sulfides. It also relates to method of preparing photofhermographic emulsions and materials using the combinations of chemical sensitizing compounds, and to methods of imaging the resulting photothermographic materials.
• Silver-containing photothemiographic imaging materials that is, them ally developable photosensitive imaging materials
• Such materials are used in a recording process wherein an image is fonried by imagewise exposure of the photothemiographic material to specific electromagnetic radiation (for example, X-radiation, or ultraviolet, visible, or infrared radiation) and developed by the use of thermal energy.
• specific electromagnetic radiation for example, X-radiation, or ultraviolet, visible, or infrared radiation
• dry silver materials generally comprise a support having coated thereon: (a) a photocatalyst (that is, a photosensitive compound such as silver halide) that upon such exposure provides a latent image in exposed grains that are capable of acting as a catalyst for the subsequent fonnation of a silver image in a development step, (b) a relatively or completely non-photosensitive source of reducible silver ions, (c) a reducing composition (usually including a developer) for the reducible silver ions, and (d) a hydrophilic or hydrophobic binder.
• a photocatalyst that is, a photosensitive compound such as silver halide
• the reducing agent for the reducible silver ions may be any compound that, in the presence of the latent image, can reduce silver ion to metallic silver and is preferably of relatively low activity until it is heated to a temperature sufficient to cause the reaction.
• developers for photothemiographic materials.
• the reducible silver ions are reduced by the reducing agent.
• photothemiographic materials upon heating, this reaction occurs preferentially in the regions sunounding the latent image. This reaction produces a negative image of metallic silver having a color that ranges from yellow to deep black depending upon the presence of toning agents and other components in the imaging layer(s).
• Photothermography differs significantly from conventional silver halide photographic materials that require processing with aqueous processing solutions.
• photothermographic imaging materials a visible image is created by heat as a result of the reaction of a developer incorporated within the material. Heating at 50°C or more is essential for this diy development.
• conventional photographic imaging materials require processing in aqueous processing baths at more moderate temperatures (from 30°C to 50°C) to provide a visible image.
• the imaged photosensitive silver halide serves as a catalyst for the physical development process involving the non-photosensitive source of reducible silver ions and the incorporated reducing agent.
• photothermographic materials require an amount of silver halide per unit area that is only a fraction of that used in conventional wet- processed photographic materials.
• all of the "chemistry" for imaging is incorporated within the material itself.
• such materials include a developer (that is, a reducing agent for the reducible silver ions) while conventional photographic materials usually do not.
• Additives that have one effect in conventional silver halide photographic materials may behave quite differently when incorporated in photothemiographic materials where the underlying chemistry is significantly more complex.
• the incoiporation of such additives as, for example, stabilizers, antifoggants, speed enhancers, supersensitizers, and spectral and chemical sensitizers in conventional photographic materials is not predictive of whether such additives will prove beneficial or detrimental in photothemiographic materials.
• a photographic antifoggant useful in conventional photographic materials to cause various types of fog when incoiporated into photothemiographic materials, or for supersensitizers that are effective in photographic materials to be inactive in photothemiographic materials.
• silver halide grains when composed only of silver and halogen atoms, have defined levels of sensitivity depending upon the levels of specific halogens, ciystal morphology (shape and structure of the crystals or grains), crystal defects, stresses, dislocations, and dopants, incoiporated within or on the crystal lattice of the silver halide.
• Chemical sensitization generally sulfur-sensitization is a process, during or after silver halide crystal formation, in which sensitization centers [for example, silver sulfide clusters such as (Ag 2 S) n are introduced onto the individual silver halide grains.
• silver sulfide specks can be introduced by direct reaction of sulfur-contributing compounds with the silver halide during various stages or after completion of silver halide grain growth. These specks usually function as shallow electron traps for the preferential formation of a latent image center. Other chalcogens (Se and Te) can function similarly. The presence of these specks increases the speed or sensitivity of the resulting silver halide grains to radiation.
• Sulfur-contributing compounds useful for this purpose include thiosulfates (such as sodium thiosulfate) and various thioureas (such as allyl thiourea, thiourea, triethyl thiourea and l,l '-diphenyl-2-thiourea) as described for example, by Sheppard et al., J Franklin Inst., 1923, pp. 196, 653, and 673, C. E. K. Mees and T. H. James, The Theory of the Photographic Process, 4 th Edition, 1977, pp.
• thiosulfates such as sodium thiosulfate
• various thioureas such as allyl thiourea, thiourea, triethyl thiourea and l,l '-diphenyl-2-thiourea
• Another method of chemical sensitization is achieved by oxidative decomposition of a sulfur-containing spectral sensitizing dye on or around preformed silver halide grains in a photothermographic emulsion as described in U.S. Patent 5,891,615 (Winslow et al.) by addition of a strong oxidizing agent such as pyridinium hydrobromide perbromide (PHP) to the emulsion.
• a strong oxidizing agent such as pyridinium hydrobromide perbromide (PHP)
• Patent 4,213,784 (Ikenoue et al.), and U.S. Patent 5,843,632 (Eshelman et al.).
• Tetrasubstituted thiourea compounds described in U.S. Patent 6,368,779 (Lynch et al.) are shown to provide increased photospeed with minimal loss in Dmin.
• Chemical sensitization to increase photospeed has also been achieved by treating the silver halide grains with gold-containing ions such as tetrachloroaurate(III) or dithiocyanatoaurate(I) for example, as described in U.S. Patent 5,220,030 (Deaton) for photographic materials.
• Au(I) is the active species in such uses (see for example, Tani, Photographic Sensitivity, Oxford University Press, 1995).
• U.S. Patent 5,858,637 also describes various gold(I) compounds that can be used as chemical sensitizers.
• U.S. Patent 6,423,481 describes highly useful gold(III)-containing chemical sensitizing compounds to increase the speed of photo thennographic materials while maintaining high Dmax and low Dmin. Photothennographic materials are constantly being redesigned to meet ever-increasing performance, storage, and manufacturing demands raised by customers, regulators, and manufacturers.
• a non-photosensitive source of reducible silver ions a non-photosensitive source of reducible silver ions
• a reducing composition for the reducible silver ions wherein the photosensitive silver halide grains have been chemically sensitized with a combination of chemical sensitizers that consists essentially of: 1) a gold (I ⁇ I)-containing compound that is represented by the following Structure GOLD: Au(III)L' 1 Y q (GOLD)
• L' represents the same or different ligands, each ligand comprising at least one heteroatom that is capable of fom ing a bond with gold, Y is an anion, r is an integer of from 1 to 8, and q is an integer of from 0 to 3, and 2) a sulfur-containing compound that is a diphenylphosphine sulfide that is represented by the following Structure PS:
• the present invention provides a X-radiation sensitive photothemiographic material comprising a support having on at least one side thereof, a photothe ⁇ nographic imaging layer having a dry coating weight of from 5 to 200 g/m", and a surface protective layer, the imaging layer comprising a hydrophobic binder and in reactive association: a. a photosensitive silver bromide or silver iodobromide, or both, b. a non-photosensitive source of reducible silver ions that includes silver behenate, c. a reducing composition for the reducible silver ions comprising a hindered phenol or an ascorbic acid, and d.
• This invention also provides a method of preparing a photothemiographic emulsion comprising: (A) providing a dispersion of a prefo ⁇ ned photosensitive silver halide grains and a non-photo-sensitive source of reducible silver ions, (B) providing one or more sulfur-containing compounds that is a diphenylphosphine sulfide compound, in association with the prefonned silver halide grains and the non-photosensitive source of reducible silver ions, the diphenylphosphine sulfide compound being represented by the Stmcture PS noted above, (C) chemically sensitizing the prefo ⁇ ned silver halide grains by decomposing the diphenylphosphine sulfide compound on or around the silver halide grains in an oxidizing environment to provide sulfur chemically sensitized photosensitive silver halide grains in reactive association with the non-photosensitive source of reducible silver ions, and (D) providing a gold(III)-containing compound in association with the
• This invention further provides a method of preparing a photothermographic material comprising: (A) providing a dispersion of preformed photosensitive silver halide grains and a non-photo-sensitive source of reducible silver ions, (B) providing a sulfur-containing compound that is a diphenylphosphine sulfide compound in association with the prefonned silver halide grains and the non-photosensitive source of reducible silver ions, the diphenylphosphine sulfide being represented by the Stmcture PS noted above, (C) chemically sensitizing the prefo ⁇ ned silver halide grains by decomposing the diphenylphosphine sulfide compound on or around the silver halide grains in an oxidizing environment to provide sulfur chemically sensitized photosensitive silver halide grains in reactive association with the non-photosensitive source of reducible silver ions, (D) providing a gold(III)-containing compound in association with the prefonned silver halide grains and the non-photosensitive source
• the present invention also provides a method for forming a visible image comprising: A) imagewise exposing the photothermographic material of the present invention to electromagnetic radiation to form a latent image, and B) simultaneously or sequentially, heating the exposed photothemiographic material to develop the latent image into a visible image.
• the method further comprises: C) positioning the exposed and heat-developed photothemiographic material with a visible image therein between a source of imaging radiation and an imageable material that is sensitive to the imaging radiation, and D) thereafter exposing the imageable material to the imaging radiation through the visible image in the exposed and heat-developed photothemiographic material to provide a visible image in the imageable material.
• the specific gold(III)-containing compounds useful in the present invention are defined by the noted Stmcture "GOLD" noted above and the specific sulfur-containing compounds are diphenylphosphine sulfides defined by Stmcture "PS" noted above. While the use of each of these types of compounds alone provides some increase in photospeed in photothemiographic emulsions, the combination of both types of compounds provides increases in both photospeed and shelf-life stability for the resulting photothemiographic materials. DETAILED DESCRIPTION OF THE INVENTION
• the photothemiographic materials of this invention can be used in black-and-white or color photothermography and in electronically generated black-and-white or color hardcopy recording.
• the absorbance of these photothemiographic materials between 350 and 450 nm is desirably low (less than 0.5), to permit their use in the graphic arts area (for example, imagesetting and phototypesetting), in the manufacture of printing plates, in contact printing, in duplicating ("duping"), and in proofing.
• the photothemiographic materials of this invention are particularly useful for medical imaging of human or animal subjects in response to visible or X-radiation for use in medical diagnosis.
• Such applications include, but are not limited to, thoracic imaging, mammography, dental imaging, orthopedic imaging, general medical radiogi-aphy, therapeutic radiography, veterinary radiogi-aphy, and auto-radiography.
• the photothemiographic materials of this invention may be used in combination with one or more phosphor intensifying screens, with phosphors incoiporated within the photothermographic emulsion, or with a combination thereof. Such materials are particularly useful for dental radiogi-aphy.
• the photothemiographic materials of this invention can be made sensitive to radiation of any suitable wavelength. Thus, in some embodiments, the materials are sensitive at ultraviolet, visible, infrared, or near infrared wavelengths, of the electromagnetic spectrum.
• the materials are preferably sensitive to radiation greater than 350 nm (such as sensitivity to fi-om 350 to 1100 nm). Increased sensitivity to a particular region of the spectrum is imparted through the use of various sensitizing dyes.
• the materials are sensitive to X-radiation directly, hi prefened embodiments, increased sensitivity to X-radiation is imparted through the use of phosphors.
• the photothemiographic materials of this invention are also useful for non-medical uses of visible or X-radiation (such as X-ray lithography and industrial radiography). In such imaging applications, it is often desirable that the photothemiographic materials be "double-sided.
• the components needed for imaging can be in one or more photothermographic layers on one side ("frontside") of the support.
• the layer(s) that contain the photosensitive photocatalyst (such as a photosensitive silver halide) or non-photosensitive source of reducible silver ions, or both, are refened to herein as photothemiographic emulsion layer(s).
• the photocatalyst and the non-photosensitive source of reducible silver ions are in catalytic proximity (that is, in reactive association with each other) and preferably are in the same emulsion layer.
• various non-imaging layers are usually disposed on the "backside” (non-emulsion or non-imaging side) of the materials, including conductive layers, an antihalation layers, protective layers, and transport enabling layers.
• various non-imaging layers can also be disposed on the "frontside” or imaging or emulsion side of the support, including protective topcoat layers, primer layers, interlayers, opacifying layers, antistatic layers, antihalation layers, acutance layers, auxiliary layers, and other layers readily apparent to one skilled in the art.
• the photothemiographic materials be "double-sided" and have the same or different photothermographic coatings (or imaging layers) on both sides of the support.
• each side can also include one or more protective topcoat layers, primer layers, interlayers, antistatic layers, acutance layers, auxiliaiy layers, anti-crossover layers, and other layers readily apparent to one skilled in the art.
• a or “an” component refers to "at least one" of that component (for example, the specific chemical sensitizing compounds).
• Heating in a substantially water-free condition as used herein means heating at a temperature of from 50°C to 250°C with little more than ambient water vapor present.
• substantially water-free condition means that the reaction system is approximately in equilibrium with water in the air and water for inducing or promoting the reaction is not particularly or positively supplied from the exterior to the material. Such a condition is described in T. H. James, The Theoiy of the Photographic Process, Fourth Edition, Eastman Kodak Company, Rochester, NY, 1977, p. 374.
• Photothei-mographic material(s) means a construction comprising at least one photothemiogi-aphic emulsion layer or a photothermographic set of emulsion layers, wherein the photosensitive silver halide and the source of reducible silver ions are in one layer and the other essential components or desirable additives are distributed, as desired, in the same layer or in an adjacent coating layer, as well as any supports, topcoat layers, image-receiving layers, blocking layers, antihalation layers, subbing or priming layers. These materials also include multilayer constmctions in which one or more imaging components are in different layers, but are in "reactive association” so that they readily come into contact with each other during imaging and/or development.
• one layer can include the non-photosensitive source of reducible silver ions and another layer can include the reducing composition, but the two reactive components are in reactive association with each other.
• imagewise exposing or “imagewise exposure” means that the material is imaged using any exposure means that provides a latent image using electromagnetic radiation. This includes, for example, by analog exposure where an image is fomied by projection onto the photosensitive material as well as by digital exposure where the image is fomied one pixel at a time such as by modulation of scamiing laser radiation.
• Catalytic proximity” or “reactive association” means that the materials are in the same layer or in adjacent layers so that they readily come into contact with each other during themial imaging and development.
• Embodision layer means a layer of a photothemiographic material that contains the photosensitive silver halide (when used) and/or non-photosensitive source of reducible silver ions. It can also mean a layer of the photothermographic material that contains, in addition to the photosensitive silver halide (when used) and/or non-photosensitive source of reducible ions, additional essential components and/or desirable additives. These layers are usually on what is known as the "frontside” of the support.
• Photocatalyst means a photosensitive compound such as silver halide that, upon exposure to radiation, provides a compound that is capable of acting as a catalyst for the subsequent development of the image- forming material.
• active ingredient means the amount or the percentage of the desired material contained in a sample. All amounts listed herein are the amount of active ingredient added.
• Ultraviolet region of the spectrum refers to that region of the spectrum less than or equal to 410 nm, and preferably from 100 nm to 410 mn, although parts of these ranges may be visible to the naked human eye. More preferably, the ultraviolet region of the spectrum is the region of from 190 to 405 nm.
• “Visible region of the spectrum” refers to that region of the spectrum of from 400 nm to 700 mn.
• “Short wavelength visible region of the spectrum” refers to that region of the spectrum of fi-om 400 nm to 450 mn.
• “Red region of the spectrum” refers to that region of the spectrum of from 600 mn to 700 nm.
• “Infrared region of the spectrum” refers to that region of the spectrum of from 700 nm to 1400 mn.
• Non-photosensitive means not intentionally light sensitive.
• the sensitometric terms "photospeed,” “speed,” or “photographic speed” (also known as sensitivity), absorbance, contrast, Dmin, and Dmax have conventional definitions known in the imaging arts. In photothe ⁇ nographic materials, Dmin is considered herein as image density achieved when the photothe iographic material is the ⁇ nally developed without prior exposure to radiation.
• the sensitometric te absorbance is another term for optical density (OD).
• Dmax is the maximum density of film in the imaged area.
• SP-2 Speed-2
• SC-2 Speed-2
• AC-1 Average Contrast- 1
• AC-2 Average Contrast-2
• D m j n the absolute value of the slope of the line joining the density points of 1.00 and 2.40 above D m j n .
• Transparent means capable of transmitting visible light or imaging radiation without appreciable scattering or absoiption.
• organic silver coordinating ligand refers to an organic molecule capable of fonning a bond with a silver atom. Although the compounds so fomied are technically silver coordination compounds they are also often refened to as silver salts.
• double-sided and double-faced coating are used to define photothermographic materials having one or more of the same or different thennally developable emulsion layers disposed on both sides (front and back) of the support.
• any substitution that does not alter the bond stmcture of the fonmila or the shown atoms within that stmcture is included within the fo ⁇ nula, unless such substitution is specifically excluded by language (such as "free of carboxy-substituted alkyl").
• substituent groups may be placed on the benzene ring stmcture, but the atoms making up the benzene ring stmcture may not be replaced.
• the terni "group” refers to chemical species that may be substituted as well as those that are not so substituted.
• group such as “alkyl group” is intended to include not only pure hydrocarbon alkyl chains, such as methyl, ethyl, /?-propyl, t-butyl, cyclohexyl, iso-octyl, and octadecyl, but also alkyl chains bearing substituents known in the art, such as hydroxyl, alkoxy, phenyl, halogen atoms (F, CI, Br, and I), cyano, nitro, amino, and carboxy.
• alkyl group includes ether and thioether groups (for example CH 3 -CH2-CH2-O-CH2- and CH 3 -CH 2 -CH2-S-CH 2 -), haloalkyl, nitroalkyl, alkylcarboxy, carboxyalkyl, carboxamido, hydroxyalkyl, sulfoalkyl, and other groups readily apparent to one skilled in the art.
• ether and thioether groups for example CH 3 -CH2-CH2-O-CH2- and CH 3 -CH 2 -CH2-S-CH 2 -
• haloalkyl for example CH 3 -CH2-CH2-O-CH2- and CH 3 -CH 2 -CH2-S-CH 2 -
• haloalkyl for example CH 3 -CH2-CH2-O-CH2- and CH 3 -CH 2 -CH2-S-CH 2 -
• haloalkyl for example CH 3 -CH2-CH2-O-CH2- and CH 3 -CH 2
• the photothemiographic materials of the present invention include one or more photocatalysts in the photothemiographic emulsion layer(s).
• Useful photocatalysts are typically photosensitive silver halides such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chloro- bromoiodide, silver chlorobromide, and others readily apparent to one skilled in the art. Mixtures of silver halides can also be used in any suitable proportion. Silver bromide and silver bromoiodide (and mixtures thereof) are more prefened, with the latter silver halide generally having up to 10 mol % silver iodide.
• the shape of the photosensitive silver halide grains used in the present invention is in no way limited.
• the silver halide grains may have any crystalline habit including, but not limited to, cubic, octahedral, tetrahedral, orthorhombic, rhombic, dodecahedral, other polyhedral, tabular, laminar, twinned, or platelet morphologies and may have epitaxial growth of crystals thereon. If desired, a mixture of these crystals can be employed.
• Silver halide grains having cubic and tabular morphology are prefened, and mixtures of both cubic and tabular grains can be used in the present invention.
• the silver halide grains may have a unifomi ratio of halide throughout.
• They may have a graded halide content, with a continuously vaiying ratio of, for example, silver bromide and silver iodide or they may be of the core-shell type, having a discrete core of one or more silver halides, and a discrete shell of one or more different silver halides.
• Core-shell silver halide grains useful in photothemiographic materials and methods of preparing these materials are described for example in U.S. Patent 5,382,504 (Shor et al.).
• Iridium and/or copper doped core-shell and non-core-shell grains are described in U.S. Patent 5,434,043 (Zou et al.) and U.S. Patent 5,939,249 (Zou).
• the photosensitive silver halide grains in the presence of a hydroxytetrazaindene (such as 4-hydroxy- 6-methyl-l ,3, 3a,7-tetrazaindene) or an N-heterocyclic compound comprising at least one mercapto group (such as l-phenyl-5-mercaptotetrazole) to provide increased photospeed.
• a hydroxytetrazaindene such as 4-hydroxy- 6-methyl-l ,3, 3a,7-tetrazaindene
• an N-heterocyclic compound comprising at least one mercapto group such as l-phenyl-5-mercaptotetrazole
• the silver halides be prefo ⁇ ned and prepared by an ex-situ process.
• the silver halide grains prepared ex-situ may then be added to and physically mixed with the non-photosensitive source of reducible silver ions. It is more preferable to form the non-photosensitive source of reducible silver ions in the presence of ex-.s7/2/-prepared silver halide.
• the source of reducible silver ions such as a long chain fatty acid silver carboxylate (commonly refened to as a silver "soap"), is formed in the presence of the preformed silver halide grains.
• Co-precipitation of the reducible source of silver ions in the presence of silver halide provides a more intimate mixture of the two materials [see, for example U.S. Patent 3,839,049 (Simons)]. Materials of this type are often refe ⁇ ed to as "prefonned soaps.”
• Preformed silver halide emulsions used in the material of this invention can be prepared by aqueous or organic processes and can be unwashed or washed to remove soluble salts. In the latter case, the soluble salts can be removed by ultrafiltration, by chill setting and leaching, or by washing the coagulum [for example, by the procedures described in U.S. Patent 2,618,556 (Hewitson et al.), U.S.
• Patent 2,614,928 (Yutzy et al), U.S. Patent 2,565,418 (Yackel), U.S. Patent 3,241,969 (Hart et al.), and U.S. Patent 2,489,341 (Waller et al.)]. It is also effective to use an in-situ process in which a halide-or a halogen-containing compound is added to an organic silver salt to partially convert the silver of the organic silver salt to silver halide.
• the compound can be one or more inorganic halides (such as zinc bromide, calcium bromide, lithium bromide, or zinc iodide) or an organic halogen-containing compound (such as N-bromo- succinimide or pyridinium hydrobromide perbromide).
• inorganic halides such as zinc bromide, calcium bromide, lithium bromide, or zinc iodide
• organic halogen-containing compound such as N-bromo- succinimide or pyridinium hydrobromide perbromide.
• Prefened silver halide grains are those having an average particle size of fi-om 0.01 to 1.5 ⁇ m, more prefened are those having an average particle size of from 0.03 to 1.0 ⁇ m, and most prefened are those having an average particle size of fi-om 0.05 to 0.8 ⁇ m.
• Those of ordinary skill in the art understand that there is a finite lower practical limit for silver halide grains that is partially dependent upon the wavelengths to which the grains are spectrally sensitized. Such a lower limit, for example, is typically from 0.01 to 0.005 ⁇ m.
• the average size of the doped photosensitive silver halide grains is expressed by the average diameter if the grains are spherical, and by the average of the diameters of equivalent circles for the projected images if the grains are cubic or in other non-spherical shapes.
• Grain size may be detem ined by any of the methods commonly employed in the art for particle size measurement. Representative methods are described by in "Particle Size Analysis,” ASTM Symposium on Light Microscopy, R. P. Loveland, 1955, pp. 94-122, and in C. E. K. Mees and T. H. James, The Theoiy of the Photographic Process, Third Edition, Macmillan, New York, 1966, Chapter 2.
• Particle size measurements may be expressed in terms of the projected areas of grains or approximations of their diameters. These will provide reasonably accurate results if the grains of interest are substantially unifo ⁇ n in shape.
• the one or more light-sensitive silver halides used in the photothe ⁇ nogi-aphic materials of the present invention are preferably present in an amount of fi-om 0.005 to 0.5 mole, more preferably from 0.01 to 0.25 mole, and most preferably from 0.03 to 0.15 mole, per mole of non-photosensitive source of reducible silver ions.
• Chemical Sensitizers A combination of compounds for chemical sensitization is used in the present invention to increase the photospeed of the photosensitive silver halides used in the photothermographic materials of the invention. At least one of the chemical sensitizing compounds is a gold(III)- containing compound represented by the following Stmcture GOLD:
• L represents the same or different ligands, each ligand comprising at least one heteroatom that is capable of forming a bond with gold, Y is an anion, r is an integer of fi-om 1 to 8, and q is an integer of fi-om 0 to 3. Mixtures of these compounds can be used if desired. More particularly, L' represents the same or different ligands that comprise at least one oxygen, nitrogen, sulfur, or phosphorous atom.
• ligands include but are not limited to, pyridine, bipyridine, terpyridine, P(phenyl) 3 , carboxylate, imine, phenol, mercaptophenol, imidazole, triazole, and dithiooxamide
• the prefened L' ligands are derived from terpyridine, P(phenyl) 3 , and salicylimine compounds.
• Y represents an appropriate counter anion having the appropriate charge.
• Useful anions include but are not limited to, halides (such as chloride and bromide), perchlorate, tetrafluoroborate, sulfate, sulfonate, methylsulfonate, -toluenesulfonate, tetrafluoroantimonate, and nitrate. Halides are prefened.
• the GOLD Stmcture also comprises r that is an integer from 1 to 8 (preferably from 1 to 3), and q is 0 or an integer fi-om 1 to 3 (preferably, 3).
• Useful gold(III)-containing chemical sensitizers can be prepared using known methods. Representative synthetic methods are described in the literature citations provided in below. In addition, some gold(III)-containing compounds can be obtained fi-om various commercial sources including Alfa Aesar (Ward Hill, MA). Particularly useful gold(III)-containing chemical sensitizers are the following Compounds Au-1 to Au-14 shown below.
• gold-containing chemical sensitizing compounds can also be used in the practice of this invention as long as at least 50 mol % of the gold-containing compounds used in the invention are those represented by Stmcture GOLD noted above.
• Another chemical sensitizing compound used in the present invention is a diphenylphosphine sulfide that can be defined using the following general Stmcture (PS):
• Phi and Ph 2 are the same or different substituted or unsubstituted phenyl groups.
• Substituents on the phenyl groups can include but are not limited to, halogen, alkyl, alkoxy, cyano, and nitro.
• and R 2 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (such as methyl, ethyl, wo-propyl, or cyclohexyl), or a substituted or unsubstituted phenyl group (such as phenyl, 4-methylphenyl, and 3-chlorophenyl).
• R 3 is a monovalent group such as a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, preferably 1 to 7 carbon atoms (such as methyl, benzyl, and methylcarbophenyl, groups), a substituted or unsubstituted aryl group (such as phenyl, naphthyl, fmanyl group), a disubstituted amino group (such as methylamino, dimethylamino, diethylamino, morpholino, or piperdino groups).
• R 3 is a substituted or unsubstituted divalent aliphatic linking group having 1 to 20 carbon, nitrogen, oxygen, or sulfur atoms in the chain (such as methylene, ethylene, propylene, polyether, or polythioether groups).
• m is 1 and R 3 is a diethylamino or a phenyl group.
• Representative compounds of Stmcture (PS) include the following PS-1 to PS-19 compounds:
• the diphenylphosphine sulfides useful in the practice of this invention can be prepared generally by alkylation of diphenylphosphine sulfide in methylene chloride at a temperature of from 0°C to room temperature for from 30 minutes to 24 hours in the presence of powdered potassium hydroxide.
• a representative synthetic method is provided below prior to the Examples.
• the following SCHEME I depicts the preparation of the diphenylphosphine sulfide compounds of this invention were L is a carbonyl group.
• the gold(III)-containing compounds described herein are incorporated into the silver halide grains by addition of a solution of the gold(III) compound during the preparation of the photothermographic emulsion. As noted below, the point of addition of the gold(III) compound appears not to be critical.
• the photothemiographic emulsions useful in the present invention can be prepared generally by: (A) providing a dispersion of a preformed photosensitive silver halide grains and a non-photo-sensitive source of reducible silver ions, (B) providing one or more diphenylphosphine sulfide compounds as described herein, in association with the preformed silver halide grains and the non-photosensitive source of reducible silver ions, (C) chemically sensitizing the prefonned silver halide grains by decomposing the diphenylphosphine sulfide compound on or around the silver halide grains in an oxidizing environment to provide sulfur chemically sensitized photosensitive silver halide grains in reactive association with the non-photo- sensitive source of reducible silver ions, and (D) providing one or more gold(III)-containing compounds as described herein in association with the prefo ⁇ ned silver halide grains and the non-photosensitive source of reducible silver ions to provide gold(III) chemically sensitized photo
• An optional additional step for this method comprises: (E) converting some of the reducible silver ions in the non-photosensitive source of reducible silver ions to photosensitive silver halide.
• the order of the steps used in preparing the final photothe ⁇ no- graphic emulsion is not critical so long as step (A) occurs first and step (C) occurs at some point after steps (A) and (B).
• steps (A) through (D), and optionally step (E) are carried out in the designated order.
• the anangement of steps can be any of the following schemes [including optional step (E)] to provide useful photothemiographic emulsions: Step (A), step (B), step (C), step (E), and step (D).
• step (B) and step (D) can be ca ⁇ ied out simultaneously
• step (D) and step (E) can be carried out simultaneously
• step (B) and step (E) can be earned out simultaneously
• step (B), step (D), and step (E) can be carried out simultaneously, all before step (C).
• step (E) is optional, it is used in prefened embodiments of the present invention. It is particularly prefened in preparing photothemiogi-aphic mate ⁇ als having a sensitivity to wavelengths greater than 600 nm
• step (B) one or more organic sulfur-containing compounds are added and suitably mixed with the photothermographic dispersion.
• Step (C) comprises decomposing the sulfur-containing diphenylphosphine sulfide compound(s) on or around the photosensitive silver halide grains in an oxidizing environment.
• Such decomposition is generally earned out using one or more oxidizing agents, and preferably a "strong" oxidizing agent, that is capable of forming species on the grains that act as the chemical sensitizer at a temperature from 10°C up to 30°C for up to 60 minutes.
• the reaction is earned out from ambient temperature (generally 20°C) up to 30°C.
• the diphenylphosphine sulfide(s) described herein becomes located on or around the surface of the silver halide grains. Oxidative decomposition of these compounds provides a residue or reaction product that reacts with silver halide grains to provide chemical sensitization sites on the grains. These sites can be in the form of silver or silver sulfide specks.
• the prefened oxidizing agents for example, PHP described below
• they may react with the diphenylphosphine sulfide compounds associated with the silver halide grain surfaces to produce or form one or more compounds (such as HSBr) that will in turn directly react with the silver halide grain surfaces to form an ordered distribution of chemically sensitized sites.
• the efficiency of the decomposition is influenced by the function and efficiency of the oxidizing agent(s), the particular sulfur-containing compound that is decomposed, the length of decomposition time, and the decomposition temperature More reactive oxidizing agents can be used at lower temperature and/or shorter times, and the converse is tme for less reactive oxidizing agents.
• Decomposition can be carried out in a single reaction or is stages where the reaction is interrupted or completed before addition of the same or different oxidizing agent.
• a single oxidizing agent can be provided in a "portioned" addition where the total amount is divided into portions and added in stages.
• Prefened oxidizing agents include hydrobromic acid salts of N-heterocyclic ring compounds (such as hydrobromic acid salts of heterocyclic compounds) that are further associated with a pair of bromine atoms. These compounds are also known as quaternary nitrogen-containing 5-, 6-, or 7-membered monocyclic or polycyclic rings that are associated with hydrobromic acid perbromide. Examples of such compounds are described as antifoggants in U.S.
• Patent 5,028,523 that is cited herein, and include compounds with substituted or unsubstituted pyridine, pyrcolidone, pynolidinone, pynolidine, phthalazinone, and phthalazine rings.
• the compounds with a pyridine ring are more prefened and a particularly useful oxidizing agent is pyridinium hydrobromide perbromide (PHP).
• PHP is used as the oxidizing agent at a temperature of from 20°C to 30°C for up to 60 minutes.
• the photothemiographic emulsion can be further modified by the addition of conventional additional chemical sensitizers that do not require oxidization, binders, toners, antifoggants, spectral sensitizing dyes, matting agents, phosphors, and other addenda commonly included within such emulsions. Further details of these compounds are provided below as well as in considerable published literature. Reducing agents (described below) can also be added at one or more times during the preparation of the photothemiographic emulsion.
• step (E) a portion of the reducible silver ions in the non-photosensitive source of reducible silver ions is converted to photosensitive silver halide by an in-situ process in which a halide-containing compound is added to an organic silver salt.
• a halide-containing compound can be inorganic halides (such as zinc bromide, calcium bromide, lithium bromide, or zinc iodide or mixtures thereof) or organic halogen-containing compounds (such as N-bromosuccinimide or pyridinium hydrobromide perbromide).
• the conversion of the reducible silver ions in step (E) can be carried out by one addition of one the noted halide- containing compounds or by multiple additions thereof at various times in the preparation of the photothermographic emulsion formulation.
• a portion of the halide-containing compound can be added before the diphenylphosphine sulfide compound and a second portion can be added after the addition of the diphenylphosphine sulfide compound.
• Different halide-containing compounds can be used in these steps if desired.
• a bromide salt can be added with an iodide salt, and then a bromide salt can be added alone. If mixtures of halides are added, they are added in a proportion to provide desired halide composition in the resulting silver halide grains.
• Zinc bromide is preferably added in the practice of this invention. It is particularly effective to use a mixture of both prefo ⁇ ned and in-situ generated silver halide.
• the halogen-containing compound(s) is added in an amount sufficient to convert from 0.1 to 10 mol % of the reducible silver ions to photosensitive silver halide.
• fi-om 0.5 to 5 mol % of the reducible silver ions are converted to photosensitive silver halide. More preferably from 1 to 3 mol % of the reducible silver ions are converted.
• the halogen-containing compound(s) is added in an amount of from 10 "4 to 10 "1 mole halogen atom per mole of non-photosensitive source of reducible silver ions.
• conversion of the reducible silver ions occurs within 30 minutes at an appropriate temperature.
• the chemical sensitizers described herein can be present in one or more imaging layer(s) disposed on the front- or back-side (or both sides) of the photothemiographic material. Preferably, they are used on all photosensitive silver halide grains within the material. It would be readily detenninable by routine experimentation as to the optimum time for adding particular chemical sensitizers to achieve the maximum speed enhancement in the photothermographic emulsion.
• the photothenriographic materials of the present invention contain silver halide grains that have been chemically sensitized with the gold(III)- containing compound(s) in an amount of fi-om 10 "8 to 10 "2 mole per mole of total silver and with the noted diphenylphosphine sulfide(s) in an amount of from 10 "6 to 1 "1 mole per mole of total silver.
• the photothermographic materials of the present invention contain silver halide grains that have been chemically sensitized with the gold(III)-containing compound(s) in an amount of from 10 "6 to 10 "5 mole per mole of total silver and the noted diphenylphosphine sulfide(s) in an amount of fi-om 10 "4 to 10 "3 mole per mole of total silver.
• the molar ratio of the gold(III)-containing compound used as a chemical sensitizer to the diphenylphosphine sulfide used as chemical sensitizer is at least 1:1 and preferably fi-om 1 :10 to 1 :5,000, and preferably fi-om 1 :1 to 1 :1,000.
• one or more "additional" chemical sensitizers may be used, if desired, to further increase photospeed.
• Such compounds may contain sulfur, tellurium, or selenium, or may comprise a compound containing gold, platinum, palladium, ruthenium, rhodium, iridium, or combinations thereof, a reducing agent such as a tin halide or a combination of any of these.
• a reducing agent such as a tin halide or a combination of any of these.
• mercaptotetrazoles and tetraazindenes as described in U.S. Patent 5,691 ,127 (Daubendiek et al.), cited herein, can be used as suitable addenda for tabular silver halide grains.
• additional sulfur sensitizers include compounds such as thiosulfates, thioureas, thiazoles, rhodanines, thiosulfates, and thioureas.
• additional chemical sensitization is achieved by oxidative decomposition of a sulfur-containing spectral sensitizing dye in the presence of a photothe ⁇ nographic emulsion as described in U.S.
• Patent 5,891,615 (Winslow et al.).
• certain substituted and unsubstituted thiourea compounds can be used as additional chemical sensitizers, such as tetra- substituted thioureas described in U.S. Patent 6,368,779 (Lynch et al.).
• Still other additional chemical sensitizers include certain tellurium- containing compounds that are described in U.S. Published Application 2002-0164549 (Lynch et al.), and certain selenium-containing compounds that are described in U.S. Patent 6,620,577 (Lynch et al.).
• the additional chemical sensitizers described above can be used in conventional amounts that generally depend upon the average size of the silver halide grains.
• the total amount is at least 10 "10 mole per mole of total silver, and preferably fi-om 10 "8 to 10 "2 mole per mole of total silver for silver halide grains having an average size of fi-om 0.01 to 2 ⁇ m.
• the upper limit can vary depending upon the compound(s) used, the level of silver halide and the average grain size, and would be readily determinable by one of ordinaiy skill in the art.
• the photosensitive silver halides used in the photothemiographic features of the invention maybe spectrally sensitized with various spectral sensitizing dyes that are known to enhance silver halide sensitivity to ultraviolet, visible, and/or infrared radiation.
• sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxanol dyes. Cyanine dyes, merocyanine dyes and complex merocyanine dyes are particularly useful.
• Spectral sensitizing dyes are chosen for optimum photosensitivity, stability, and ease of synthesis. They may be added at any stage in chemical finishing of the photothermographic emulsion. Spectral sensitization is generally carried out by adding one or more spectral sensitizing dyes to the photothe ⁇ nogi-aphic emulsion after chemical sensitization is achieved. For example, spectral sensitizers can be added after step (C) noted above for the methods of making the photothe ⁇ nograph.ic emulsions and materials. Such spectral sensitizers can provide spectral sensitization in the range of from 350 to HOO nm. Suitable sensitizing dyes such as those described in U.S. Patent
• Patent 5,508,162 (Dankosh), U.S. Patent 5,510,236 (Dankosh), U.S. Patent 5,541,054 (Miller et al.), JP Kokai 2000-063690 (Tanaka et al.), JP Kokai 2000-112054 (Fukusaka et al.), JP Kokai 2000-273329 (Tanaka et al.), JP Kokai 2001-005145 (Arai), JP Kokai 2001-064527 (Oshiyama et al.), and JP Kokai 2001-154305 (Kita et al.), can be used in the practice of the invention.
• Patent 4,678,741 (Yamada et al.), U.S. Patent 4,720,451 (Shuto et al.), U.S. Patent 4,818,675 (Miyasaka et al.), U.S. Patent 4,945,036 (Arai et al.), and U.S. Patent 4,952,491 ( ⁇ ishikawa et al).
• spectral sensitizing dyes that decolorize by the action of light or heat. Such dyes are described in U.S.
• Spectral sensitizing dyes may be used singly or in combination.
• the dyes are selected for the potpose of adjusting the wavelength distribution of the spectral sensitivity, and for the purpose of supersensitization.
• spectral sensitizing dye is generally 10 "10 to 10 " mole, and preferably, 10 "7 to 10 "2 mole per mole of silver halide.
• the non-photosensitive source of reducible silver ions used in the photothemiographic materials of this invention can be any metal-organic compound that contains reducible silver (1+) ions.
• Such compounds are generally silver salts of silver coordinating ligands.
• it is an organic silver salt that is comparatively stable to light and fonns a silver image when heated to 50°C or higher in the presence of an exposed photocatalyst (such as silver halide, when used in a photothemiographic material) and a reducing composition.
• Silver salts of organic acids including silver salts of long-chain carboxylic acids are prefened.
• the chains typically contain 10 to 30, and preferably 15 to 28, carbon atoms.
• Suitable organic silver salts include silver salts of organic compounds having a carboxylic acid group. Examples thereof include a silver salt of an aliphatic carboxylic acid or a silver salt of an aromatic carboxylic acid.
• Prefened examples of the silver salts of aliphatic carboxylic acids include silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caprate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartarate, silver furoate, silver linoleate, silver butyrate, silver camphorate, and mixtures thereof.
• at least silver behenate is used alone or in mixtures with other silver carboxylates.
• Representative silver salts of aromatic carboxylic acid and other carboxylic acid group-containing compounds include, but are not limited to, silver benzoate, silver substituted-benzoates (such as silver 3,5-dihydroxy-benzoate, silver o-mefhylbenzoate, silver w-methylbenzoate, silver /?-methylbenzoate, silver 2,4-dichlorobenzoate, silver acetamidobenzoate, silver -phenylbenzoate), silver tamiate, silver phthalate, silver terephthalate, silver salicylate, silver phenylacetate, and silver pyi-omellitate.
• silver substituted-benzoates such as silver 3,5-dihydroxy-benzoate, silver o-mefhylbenzoate, silver w-methylbenzoate, silver /?-methylbenzoate, silver 2,4-dichlorobenzoate, silver acetamidobenzoate, silver -phenylbenzoate
• silver tamiate silver
• Silver salts of aliphatic carboxylic acids containing a thioether gi'oup as described in U.S. Patent 3,330,663 are also useful.
• Soluble silver carboxylates comprising hydrocarbon chains incoiporating ether or thioether linkages, or sterically hindered substitution in the ⁇ - (on a hydrocarbon group) or ortho- (on an aromatic group) position, and displaying increased solubility in coating solvents and affording coatings with less light scattering can also be used.
• Such silver carboxylates are described in U.S. Patent 5,491,059 (Whitcomb). Mixtures of any of the silver salts described herein can also be used if desired.
• Silver salts of dicarboxylic acids are also useful. Such acids may be aliphatic, aromatic, or heterocyclic. Examples of such acids include, for example, phthalic acid, glutamic acid, or homo-phthalic acid. Silver salts of sulfonates are also useful in the practice of this invention. Such materials are described for example in U.S. Patent 4,504,575 (Lee). Silver salts of sulfosuccinates are also useful as described for example in EP 0 227 141A1 (Leenders et al.). Silver salts of compounds containing mercapto or thione groups and derivatives thereof can also be used.
• Prefened examples of these compounds include, but are not limited to, a heterocyclic nucleus containing 5 or 6 atoms in the ring, at least one of which is a nitrogen atom, and other atoms being carbon, oxygen, or sulfur atoms.
• heterocyclic nuclei include, but are not limited to, triazoles, oxazoles, thiazoles, thiazolines, imidazoles, diazoles, pyridines, and triazines.
• silver salts include, but are not limited to, a silver salt of 3-mercapto-4-phenyl-l,2,4-triazole, a silver salt of 5-carboxylic- l-methyl-2-phenyl-4-thiopyridine, a silver salt of mercapto triazine, a silver salt of 2-mercaptobenzoxazole, silver salts as described in U.S.
• Patent 4,123,274 (Knight et al.) (for example, a silver salt of a 1,2,4-mercaptofhiazole derivative, such as a silver salt of 3-amino-5-benzylthio-l,2,4-thiazole), and a silver salt of thione compounds [such as a silver salt of 3-(2-carboxyethyl)-4-methyl-4-thiazoline- 2-thione as described in U.S. Patent 3,785,830 (Sullivan et al.)].
• a silver salt of a 1,2,4-mercaptofhiazole derivative such as a silver salt of 3-amino-5-benzylthio-l,2,4-thiazole
• thione compounds such as a silver salt of 3-(2-carboxyethyl)-4-methyl-4-thiazoline- 2-thione as described in U.S. Patent 3,785,830 (Sullivan et al.)].
• Examples of other useful silver salts of mercapto or thione substituted compounds that do not contain a heterocyclic nucleus include but are not limited to, a silver salt of thioglycolic acids such as a silver salt of an S-alkyl- thioglycolic acid (wherein the alkyl group has from 12 to 22 carbon atoms), a silver salt of a dithiocarboxylic acid such as a silver salt of a dithioacetic acid, and a silver salt of a thioamide.
• a silver salt of a compound containing an imino group is prefened, especially in aqueous-based imaging formulations.
• Prefened examples of these compounds include, but are not limited to, silver salts of benzotriazole and substituted derivatives thereof (for example, silver methyl - benzotriazole and silver 5-chlorobenzotriazole), silver salts of 1 ,2,4-triazoles or 1-77-tetrazoles such as phenylmercaptotetrazole as described in U.S. Patent 4,220,709 (deMauriac), and silver salts of imidazoles and imidazole derivatives as described in U.S. Patent 4,260,677 (Winslo et al.).
• Particularly useful silver salts of this type are the silver salts of benzotriazole and substituted derivatives thereof.
• a silver salt of benzotriazole is prefened in aqueous-based photothermographic fo ⁇ nulations.
• silver salts of acetylenes can also be used as described, for example in U.S. Patent 4,761,361 (Ozaki et al.) and U.S. Patent 4,775,613 (Hirai et al.).
• Organic silver salts that are particularly useful in organic solvent- based photothermographic materials include silver carboxylates (both aliphatic and aromatic carboxylates), silver triazolates, silver sulfonates, silver sulfosuccinates, and silver acetylides.
• Silver salts of long-chain aliphatic carboxylic acids containing 15 to 28, carbon atoms (and including silver behenate) are particularly prefened. It is also convenient to use silver half soaps.
• a prefened example of a silver half soap is an equimolar blend of silver carboxylate and carboxylic acid, which analyzes for 14.5% by weight solids of silver in the blend and which is prepared by precipitation from an aqueous solution of an ammonium or an alkali metal salt of a commercially available fatty carboxylic acid, or by addition of the free fatty acid to the silver soap.
• a silver carboxylate full soap containing not more than 15% of free fatty carboxylic acid and analyzing for 22% silver, can be used.
• Non-photosensitive sources of reducible silver ions can also be provided as core-shell silver salts such as those described in U.S. Patent 6,355,408 (Whitcomb et al.). These silver salts include a core comprised of one or more silver salts and a shell having one or more different silver salts.
• non-photosensitive reducible silver ions are the silver dimer compounds that comprise two different silver salts as described in U.S. Patent 6,472,131 (Whitcomb).
• Such non-photosensitive silver dimer compounds comprise two different silver salts, provided that when the two different silver salts comprise straight-chain, saturated hydrocarbon groups as the silver coordinating ligands, those ligands differ by at least 6 carbon atoms.
• Still other useful sources of non-photosensitive reducible silver ions in the practice of this invention are the silver core-shell compounds comprising a primary core comprising one or more photosensitive silver halides, or one or more non-photosensitive inorganic metal salts or non-silver containing organic salts, and a shell at least partially covering the primary core, wherein the shell comprises one or more non-photosensitive silver salts, each of which silver salts comprises a organic silver coordinating ligand.
• Such compounds are described in copending and commonly assigned U.S. Serial No. 10/208,603 (filed July 30, 2002 by Bokhonov, Burleva, Whitcomb, Howlader, andchter).
• the non-photosensitive source of reducible silver ions can include various mixtures of the various silver salt compounds described herein, in any desirable proportions.
• the photocatalyst and the non-photosensitive source of reducible silver ions must be in catalytic proximity (that is, reactive association). It is prefened that these reactive components be present in the same emulsion layer.
• the one or more non-photosensitive sources of reducible silver ions are preferably present in an amount of 5% by weight to 70% by weight, and more preferably, 10% to 50% by weight, based on the total dry weight of the emulsion layers.
• the amount of the sources of reducible silver ions is generally present in an amount of from 0.001 to 0.2 mol/m" of the diy photothemiographic material, and preferably fi-om 0.01 to 0.O5 mol/m 2 of that material.
• the total amount of silver (from all silver sources) in the photothemiographic materials is generally at least 0.002 mol/m" and preferably fi-om 0.01 to 0.05 mol/m 2 .
• the reducing agent (or reducing agent composition comprising two or more components) for the source of reducible silver ions can be any material, preferably an organic material, that can reduce silver (1+) ion to metallic silver.
• Conventional photographic developers can be used as reducing agents, including aromatic di- and tri-hydroxy compounds (such as hydro- quinones, gallatic acid and gallic acid derivatives, catechols, and pyrogallols), aminophenols (for example, N-methylaminophenol), -phenylenediamines, alkoxynaphthols (for example, 4-methoxy-l-naphthol), pyrazolidin-3-one type reducing agents (for example PHENIDONE ® ), pyrazolin-5-ones, polyhydroxy spiro-bis-indanes, indan-l,3-dione derivatives, hydroxytetrone acids, hydroxy- tetronimides, hydroxylamine derivatives such as for example those described in U.
• Patent 4,082,901 (Laridon et al.), hydrazine derivatives, hindered phenols, amidoximes, azines, reductones (for example, ascorbic acid and ascorbic acid derivatives), leuco dyes, and other materials readily apparent to one skilled in the art.
• ascorbic acid reducing agents are prefened.
• An "ascorbic acid” reducing agent (also refe ⁇ ed to as a developer or developing agent) means ascorbic acid, complexes, and derivatives thereof.
• Ascorbic acid developing agents are described in a considerable number of publications in photographic processes, including U.S. Patent 5,236,816 (Purol et al.) and references cited therein.
• Useful ascorbic acid developing agents include ascorbic acid and the analogues, isomers and derivatives thereof.
• Such compounds include, but are not limited to, D- or L- ascorbic acid, sugar-type derivatives thereof (such as sorboascorbic acid, ⁇ -lactoascorbic acid, 6-desoxy-L-ascorbic acid, L-rhamnoascorbic acid, imino- 6-desoxy-L-ascorbic acid, glucoascorbic acid, fucoascorbic acid, glucohepto- ascorbic acid, maltoascorbic acid, L-arabosascorbic acid), sodium ascorbate, potassium ascorbate, isoascorbic acid (or L-eiythroascorbic acid), and salts thereof (such as alkali metal, ammonium or others known in the art), endiol type ascorbic acid, an enaminol type ascorbic acid, a thioenol type
• Patent 5,498,511 (Yamashita et al.), EP 0 585 792A1 (Passarella et al.), EP 0 573 700A1 (Lingier et al.), EP 0 588 408A1 (Hieronymus et al.), U.S. Patent 5,089,819 (Knapp), U.S. Patent 5,278,035 (Knapp), U.S. Patent 5,384,232 (Bishop et al.), U.S. Patent 5,376,510 (Parker et al.), Japanese Kokai 7-56286 (Toyoda), U.S. Patent 2,688,549 (James et al.), and Research Disclosure, item 37152, March 1995.
• D-, L-, or D,L-ascorbic acid and alkali metal salts thereof) or isoascorbic acid (or alkali metal salts thereof) are preferred. Mixtures of these developing agents can be used if desired.
• hindered phenol reducing agents are prefened.
• the reducing agent composition comprises two or more components such as a hindered phenol developer and a co-developer that can be chosen from the various classes of co-developers and reducing agents described below.
• Ternary developer mixtures involving the further addition of contrast enhancing agents are also useful. Such contrast enhancing agents can be chosen from the various classes of reducing agents described below.
• Hindered phenol reducing agents are prefened (alone or in combination with one or more high-contrast co-developing agents and co-developer contrast enhancing agents).
• Hindered phenol reducing agents are compounds that contain only one hydroxy group on a given phenyl ring and have at least one additional substituent located ortho to the hydroxy group.
• Hindered phenol reducing agents may contain more than one hydroxy group as long as each hydroxy group is located on different phenyl rings.
• Hindered phenol reducing agents include, for example, binaphthols (that is dihydroxybinaphthyls), biphenols (that is dihydroxy- biphenyls), bis(hydroxynaphthyl)methanes, bis(hydroxyphenyl)methanes (that is bisphenols), hindered phenols, and hindered naphthols, each of which may be variously substituted.
• Representative binaphthols include, but are not limited, to l,l '-bi-2-naphthol, l,l '-bi-4-methyl-2-naphthol and 6,6' -dibromo-bi-2-naphthol.
• biphenols include, but are not limited, to 2,2'-dihydiOxy-3,3'-di-t-butyl-5,5-dimethylbiphenyl, 2,2'-dihydroxy- 3,3',5,5'-tetra-t-butylbiphenyl, 2,2 , -dihydroxy-3,3'-di-t-butyl-5,5'-dichloro- biphenyl, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-4-methyl-6-7?-hexylphenol, 4,4'-dihydiOxy-3,3',5,5 , -tetra-t-butylbiphenyl and 4,4'-dihydroxy-3,3',5,5 , -tetra- methylbiphen
• Representative bis(hydroxynaphthyl)methanes include, but are not limited to, 4,4 , -methylenebis(2-methyl-l-naphthol).
• Representative bis(hydroxynaphthyl)methanes include, but are not limited to, 4,4 , -methylenebis(2-methyl-l-naphthol).
• bis(hydroxyphenyl)methanes include, but are not limited to, bis(2-hydroxy-3-/-butyl-5-methylphenyl)methane (CAO-5), 1,1 '-bis(2-hydiOxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane (NONOX or PERMANAX ® WSO), l,r-bis(3,5-di-t-butyl-4-hydroxyphenyl)methane, 2,2'-bis(4-hydroxy-3-methylphenyl)propane, 4,4"-ethylidene-bis(2-t-butyl- 6-methylphenol), 2,2 , -isobutylidene-bis(4,6-dimethylphenol) (LOWINOX' 6> 221B46), and 2,2'-bis(3,5-dimethyl-4-hydroxyphenyl)propane.
• CAO-5 bis(2-hydroxy-3-/-butyl-5-methylphenyl)me
• Representative hindered phenols include, but are not limited to, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2,4-di-t-butylphenol, 2,6-dichlorophenol, 2,6-dimethylphenol and 2-t-butyl-6-methylphenol.
• Representative hindered naphthols include, but are not limited to, 1-naphthol, 4-methyl-l-naphthol, 4-methoxy-l-naphthol, 4-chloro-l-naphthol and 2-methyl-l-naphthol.
• Patent 5,262,295 (noted above). Mixtures of hindered phenol reducing agents can be used if desired. Still another useful class of reducing agents are polyhydroxy spiro-bis-indane compounds described as photographic tam ing agents in U.S. Patent 3,440,049 (Moede). Examples include 3,3,3',3'-tetramethyl-5,6,5',6'-tetra- hydroxy-1 , 1 '-spiro-bis-indane (called indane I) and 3,3,3',3'-tetramethyl- 4,6,7,4',6',7'-hexahydroxy-l, -spiro-bis-indane (called indane II).
• indane I 3,3,3',3'-tetramethyl-5,6,5',6'-tetra- hydroxy-1 , 1 '-spiro-bis-indane
• indane II 3,3,3',3'-tetramethyl- 4,6,7,4
• reducing agents that can be used as developers are substituted hydrazines including the sulfonyl hydrazides described in U.S. Patent 5,464,738 (Lynch et al.). Still other useful reducing agents are described, for example, in U.S. Patent 3,074,809 (Owen), U.S. Patent 3,094,417 (Workman), U.S. Patent 3,080,254 (Grant, Jr.), and U.S. Patent 3,887,417 (Klein et al.). Auxiliary reducing agents may be useful as described in U.S. Patent 5,981,151 (Leenders et al.).
• amidoximes such as phenylamidoxime, 2-thienyl- amidoxime and jp-phenoxyphenylamidoxime, azines (for example, 4-hydroxy -3,5-dimethoxybenzaldehydrazine), a combination of aliphatic carboxylic acid aryl hydrazides and ascorbic acid [such as 2,2 , -bis(hydiOxymethyl)-piOpionyl- ⁇ -phenyl hydrazide in combination with ascorbic acid], a combination of polyhydroxy- benzene and hydroxylamine, a reductone and/or a hydrazine [for example, a combination of hydroquinone and bis(ethoxyethyl)hydroxylamine], piperidino- hexose reductone or fo ⁇ nyl-4-methylphenylhydrazine, hydroxamic acids (such as phenylhydroxamic acid,
• Useful co-developer reducing agents can also be used as described for example, in U.S. Patent 6,387,605 (Lynch et al.).
• these compounds include, but are not limited to, 2,5-dioxo-cyclopentane carbox- aldehydes, 5-(hydroxymethylene)-2,2-dimethyl-l,3-dioxane-4,6-diones, 5-(hydiOxymethylene)-l,3-dialkylbarbituric acids, and 2-(ethoxymethylene)- 1 H-indene- 1 ,3 (2H)-diones.
• Additional classes of reducing agents that can be used as co-developers are trityl hydrazides and fonnyl phenyl hydrazides as described in U.S. Patent 5,496,695 (Simpson et al.), 2-substituted malondialdehyde compounds as described in U.S. Patent 5,654,130 (Mu ⁇ ay), and 4-substituted isoxazole compounds as described in U.S. Patent 5,705,324 (Mu ⁇ ay). Additional developers are described in U.S. Patent 6,100,022 (Inoue et al.). Yet another class of co-developers includes substituted aciylonitrile compounds that are described in U.S.
• Patent 5,635,339 (Murray) and U.S. Patent 5,545,515 (Mu ⁇ ay et al.).
• Examples of such compounds include, but are not limited to, the compounds identified as HET-01 and HET-02 in U.S. Patent 5,635,339 (noted above) and CN-01 through CN-13 in U.S. Patent 5,545,515 (noted above).
• Particularly useful compounds of this type are (hydroxymethylene)cyanoacetates and their metal salts.
• Various contrast enhancing agents can be used in some photo- themiographic materials with specific co-developers.
• useful contrast enhancing agents include, but are not limited to, hydroxylamines (including hydroxylamine and alkyl- and aryl-substituted derivatives thereof), alkanolamines and ammonium phthalamate compounds as described for example, in U.S. Patent 5,545,505 (Simpson), hydroxamic acid compounds as described for example, in U.S. Patent 5,545,507 (Simpson et al.), N-acylhydrazine compounds as described for example, in U.S. Patent 5,558,983 (Simpson et al.), and hydrogen atom donor compounds as described in U.S. Patent 5,637,449 (Ha ⁇ ing et al.).
• Aromatic di- and tri-hydroxy reducing agents can also be used in combination with hindered phenol reducing agents either together or in or in combination with one or more high-contrast co-developing agents and co-developer contrast-enhancing agents).
• the reducing agent (or mixture thereof) described herein is generally present as 1 to 10% (dry weight) of the emulsion layer. In multilayer constructions, if the reducing agent is added to a layer other than an emulsion layer, slightly higher proportions, of from 2 to 15 weight % may be more desirable. Any co-developers may be present generally in an amount of fi-om 0.001% to 1.5% (diy weight) of the emulsion layer coating.
• one or more reducing agents can be used that can be oxidized directly or indirectly to fonn or release one or more dyes.
• the dye-fo ⁇ ning or releasing compound may be any colored, colorless, or lightly colored compound that can be oxidized to a colored form, or to release a prefonned dye when heated, preferably to a temperature of from 80°C to 250°C for a duration of at least 1 second.
• the dye can diffuse through the imaging layers and interlayers into the image-receiving layer of the photothermographic material.
• Leuco dyes or "blocked" leuco dyes are one class of dye-fo ⁇ ning compounds (or “blocked” dye-forming compounds) that form and release a dye upon oxidation by silver ion to form a visible color image in the practice of the present invention.
• Leuco dyes are the reduced fonn of dyes that are generally colorless or very lightly colored in the visible region (optical density of less than 0.2). Thus, oxidation provides a color change that is from colorless to colored, an optical density increase of at least 0.2 units, or a substantial change in hue.
• leuco dyes include, but are not limited to, chromogenic leuco dyes (such as indoaniline, indophenol, or azomethine dyes), imidazole leuco dyes such as 2-(3,5-di-t-butyl-4-hydroxy- phenyl)-4,5-diphenylimidazole as described for example in U.S. Patent 3,985,565 (Gabrielson et al.), dyes having an azine, diazine, oxazine, or thiazine nucleus such as those described for example in U.S. Patent 4,563,415 (Brown et al.), U.S.
• chromogenic leuco dyes such as indoaniline, indophenol, or azomethine dyes
• imidazole leuco dyes such as 2-(3,5-di-t-butyl-4-hydroxy- phenyl)-4,5-diphenylimidazo
• Patent 4,622,395 Bellus et al.
• U.S. Patent 4,710,570 Thien
• U.S. Patent 4,782,010 Mader et al.
• benzylidene leuco compounds as described for example in U.S. Patent 4,932,792 (Grieve et al.).
• Further details about the chromogenic leuco dyes noted above can be obtained from U.S. Patent 5,491,059 (noted above, Column 13) and references noted therein.
• Another useful class of leuco dyes includes what are known as "aldazine” and "ketazine” leuco dyes that are described for example in U.S.
• Patent 4,587,211 Ishida et al.
• U.S. Patent 4,795,697 Vogel et al.
• Still another useful class of dye-releasing compounds includes those that release diffusible dyes upon oxidation. These are known as preformed dye release (PDR) or redox dye release (RDR) compounds. In such compounds, the reducing agents release a mobile prefomied dye upon oxidation. Examples of such compounds are described in U.S. Patent 4,981,775 (Swain).
• the reducing agent can be a compound that releases a conventional photographic dye forming color coupler or developer upon oxidation as is known in the photographic art.
• the dyes that are fomied or released can be the same in the same or different imaging layers.
• a difference of at least 60 nm in reflective maximum absorbance is prefened. More preferably, this difference is fi-om 80 to 100 nm. Further details about the various dye absorbance are provided in U.S.
• the total amount of one or more dye- forming or releasing compound that can be incoiporated into the photothermographic materials of this invention is generally from 0.5 to 25 weight % of the total weight of each imaging layer in which they are located. Preferably, the amount in each imaging layer is from 1 to 10 weight %, based on the total dry layer weight.
• the useful relative proportions of the leuco dyes would be readily known to a skilled worker in the art.
• the photothemiographic materials of this invention can also contain other additives such as shelf-life stabilizers, antifoggants, contrast enhancers, development accelerators, acutance dyes, post-processing stabilizers or stabilizer precursors, thermal solvents (also known as melt formers), and other image-modifying agents as would be readily apparent to one skilled in the art.
• additives such as shelf-life stabilizers, antifoggants, contrast enhancers, development accelerators, acutance dyes, post-processing stabilizers or stabilizer precursors, thermal solvents (also known as melt formers), and other image-modifying agents as would be readily apparent to one skilled in the art.
• heteroaiOinatic mercapto compounds or heteroaromatic disulfide compounds of the fo ⁇ nulae Ar-S-M 1 and Ar-S-S-Ar wherein M 1 represents a hydrogen atom or an alkali metal atom and Ar represents a heteroaromatic ring or fused heteroaromatic ring containing one or more of nitrogen, sulfur, oxygen, selenium, or tellurium atoms.
• the heteroaromatic ring comprises benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline, or quinazolinone.
• Compounds having other heteroaromatic rings and compounds providing enhanced sensitization at other wavelengths are also envisioned to be suitable.
• heteroaromatic mercapto compounds are described as supersensitizers for infrared photothermographic materials in EP 0 559 228B1 (Philip Jr. et al.). These compounds are useful as addenda when added to the emulsion along with the sensitizing dye (where they are especially beneficial with red and infrared sensitive films), and especially when used in organic [for example, poly( vinyl butyral)] or aqueous latex binders.
• the heteroaromatic ring may also cany substituents.
• prefened substituents are halo groups (such as bromo and chloro), hydroxy, amino, carboxy, alkyl groups (for example, of 1 or more carbon atoms and preferably 1 to 4 carbon atoms), and alkoxy groups (for example, of 1 or more carbon atoms and preferably of 1 to 4 carbon atoms).
• Heteroaromatic mercapto compounds are most prefened. Examples of prefened heteroaromatic mercapto compounds are 2-mercaptobenz- imidazole, 2-mercapto-5-methylbenzimidazole, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, and mixtures thereof.
• a heteroaromatic mercapto compound is generally present in an emulsion layer in an amount of at least 0.0001 mole per mole of total silver in the emulsion layer. More preferably, the heteroaromatic mercapto compound is present within a range of 0.001 mole to 1.0 mole, and most preferably, 0.005 mole to 0.2 mole, per mole of total silver.
• the photothe ⁇ nogi-aphic materials of this invention can be further protected against the production of fog and can be stabilized against loss of sensitivity during storage. While not necerney for the practice of the invention, it may be advantageous to add mercury (2+) salts to the emulsion layer(s) as an antifoggant. Prefened mercury (2+) salts for this purpose are mercuric acetate and mercuric bromide. Other useful mercury salts include those described in U.S.
• Patent 2,728,663 (Allen).
• Other suitable antifoggants and stabilizers that can be used alone or in combination include thiazolium salts as described in U.S. Patent 2,131,038
• Patent 2,886,437 (Piper), triazaindolizines as described in U.S. Patent 2,444,605
• Patent 2,839,405 (Jones), thiuronium salts as described in U.S. Patent 3,220,839
• Patent 5,374,514 (Kirk et al.), and 2-(tribiOmomethylsulfonyl)quinoline compounds as described in U.S. Patent 5,460,938 (Kirk et al.).
• Stabilizer precursor compounds capable of releasing stabilizers upon application of heat during development can also be used. Such precursor compounds are described in for example, U.S. Patent 5,158,866 (Simpson et al.),
• Patent 6,083,681 (Lynch et al.).
• Other antifoggants are hydrobromic acid salts of heterocyclic compounds (such as pyridinium hydrobromide perbromide) as described, for example, in U.S. Patent 5,028,523 (Skoug), benzoyl acid compounds as described, for example, in U.S. Patent 4,784,939 (Pham), substituted propenenitrile compounds as described, for example, in U.S. Patent 5,686,228 (Mu ⁇ ay et al), silyl blocked compounds as described, for example, in U.S. Patent 5,358,843 (Sakizadeh et al.), vinyl sulfones as described, for example, in U.S.
• the photothermographic materials of the present invention include one or more polyhalo antifoggants that include one or more polyhalo substituents including but not limited to, dichloro, dibromo, trichloro, and tribromo groups.
• the antifoggants can be aliphatic, alicyclic or aromatic compounds, including aromatic heterocyclic and carbocyclic compounds.
• Particularly useful antifoggants are polyhalo antifoggants, such as those having a -SO 2 C(X') 3 group wherein X' represents the same or different halogen atoms.
• the photothermographic materials of this invention also include one or more the ⁇ nal solvents (or melt formers).
• Such compounds include, but are not limited to, salicylanilide, phthalimide, N-hydroxyphthalimide, N-potassium-phthalimide, succinimide, N-hydroxy-l,8-naphthalimide, phthalazine, l-(2H)-phthalazinone, 2-acetylphfhalazinone, benzanilide, dimethylurea, D-sorbitol, and benzene- sulfonamide. Combinations of these compounds can also be used including a combination of succinimide and dimethylurea.
• Known themial solvents are disclosed, for example, in U.S. Patent 3,438,776 (Yudelson), U.S.
• Patent 5,250,386 (Aono et al), U.S. Patent 5,368,979 (Freedman et al.), U.S. Patent 5,716,772 (Taguchi et al.), and U.S. Patent 6,013,420 (Windender).
• a base-release agent or base precursor as employed herein is intended to include compounds which upon heating in the photothermographic material provide a more effective reaction between the described photosensitive silver halide, and the image-fo ⁇ ning combination comprising a silver salt and the silver halide developing agent.
• Representative base-release agents or base precursors include guanidinium compounds, such as guanidinium trichloroacetate, and other compounds that are known to release a base but do not adversely affect photographic silver halide materials, such as phenylsulfonyl acetates. Further details are provided in U.S. Patent 4,123,274 (Knight et al.).
• a range of concentration of the base-release agent or base precursor is useful in the described photothermographic materials. The optimum concentration of base-release agent or base precursor will depend upon such factors as the desired image, particular components in the photothemiographic material, and processing conditions. The use of "toners" or derivatives thereof that improve the image are highly desirable components of the photothermographic materials.
• Toners are compounds that when added to the photothennographic imaging layer(s) shift the color of the developed silver image from yellowish-orange to brown-black or blue-black.
• one or more toners described herein are present in an amount of 0.01% by weight to 10%, and more preferably 0.1% by weight to 10% by weight, based on the total dry weight of the layer in which it is included.
• Toners may be incoiporated in the photothennographic emulsion layer(s) or in an adjacent layer. Compounds useful as toners are described for example in U.S. Patent 3,080,254 (Grant, Jr.), U.S. Patent 3,847,612 (Winslow), U.S.
• Patent 4,123,282 (Winslow), U.S. Patent 4,082,901 (Laridon et al), U.S. Patent 3,074,809 (Owen), U.S. Patent 3,446,648 (Workman), U.S. Patent 3,844,797 (Willems et al), U.S. Patent 3,951,660 (Hagemann et al), U.S. Patent 5,599,647 (Defieuw et al.) and GB 1,439,478 (AGFA). Phthalazine and phthalazine derivatives [such as those described in U.S.
• Patent 6,146,822 (Asanuma et al.)], phthalazinone, and phthalazinone derivatives are particularly useful toners. Additional useful toners are substituted and unsubstituted mercaptotriazoles as described for example in U.S. Patent 3,832,186 (Masuda et al.), U.S. Patent 6,165,704 (Miyake et al.), U.S. Patent 5,149,620 (Simpson et al.), and commonly assigned U.S. Publication No. 2004/0013985 (Lynch et al.) and U.S. Serial No. 10/192,944 (filed July 11 , 2002 by Lynch, Ulrich, and Zou).
• phthalazine compounds described in commonly assigned U.S. Patent 6,605,418 Radsden et al.
• the triazine thione compounds described in U.S. Patent 6,703,191 (Lynch et al.)
• the heterocyclic disulfide compounds described in U.S. Patent 6,737,227 (Lynch et al.).
• toners include, but are not limited to, phthalimide and
• N-hydroxyphthalimide N-hydroxyphthalimide, cyclic imides (such as succinimide), pyrazoline-5-ones, quinazolinone, 1 -phenylurazole, 3-phenyl-2-pyrazoline-5-one, and 2,4-thiazolidinedione
• naphthalimides such as N-hydroxy-l,8-naphthalimide
• cobalt complexes such as hexaaminecobalt(3+) trifluoroacetate
• mercaptans such as 3-mercapto-l,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto- 4,5-diphenyl-l,2,4-triazole and 2,5-dimercapto-l,3,4-thiadiazole
• N-(amino- methyl)a ⁇ yldicarboximides such as ( ⁇ , ⁇ -dimethylaminomethyl)phthalimide
• Patent 5,817,598 (Defieuw et al.), pyrimidines and asym-triazines (such as 2,4-dihydiOxypyrimidine, 2-hydroxy- 4-aminopyrimidine and azauracil) and tetraazapentalene derivatives [such as 3,6-dimercapto-l,4-diphenyl-7H, ⁇ H-2,3a,5,6a-tetraazapentalene and l,4-di-(o-chlorophenyl)-3,6-dimercapto-iH, ' i'H-2,3a,5,6a-tetraazapentalene].
• pyrimidines and asym-triazines such as 2,4-dihydiOxypyrimidine, 2-hydroxy- 4-aminopyrimidine and azauracil
• tetraazapentalene derivatives such as 3,6-dimercapto-l,
• the photothennographic materials of this invention can also include one or more image stabilizing compounds that are usually incoiporated in a "backside" layer.
• image stabilizing compounds can include, but are not limited to, phthalazinone and its derivatives, pyridazine and its derivatives, benzoxazine and benzoxazine derivatives, benzothiazine dione and its derivatives, and quinazoline dione and its derivatives, particularly as described in commonly assigned U.S. Patent 6,599,685 (Kong).
• backside image stabilizers include, but are not limited to, anthracene compounds, coumarin compounds, benzophenone compounds, benzotriazole compounds, naphthalic acid imide compounds, pyrazoline compounds, or compounds described for example, in U.S. Patent 6,465,162 (Kong et al.) and GB 1,565,043 (Fuji Photo).
• Phosphors In some embodiments, it is also effective to incorporate X-radiation-sensitive phosphors in the chemically sensitized photothemiographic emulsions and materials described herein.
• Organic solvent-based emulsions and materials are described in U.S. Patent 6,440,649 (Simpson et al.) and aqueous- based emulsions and materials are described in U.S. Patent 6,573,033 (Simpson et al.).
• Any conventional or useful phosphor can be used, singly or in mixtures, in the practice of this invention. More specific details of useful phosphors are provided as follows.
• Phosphors are materials that emit infrared, visible, or ultraviolet radiation upon excitation.
• An intrinsic phosphor is a material that is naturally (that is, intrinsically) phosphorescent.
• An "activated" phosphor is one composed of a basic material that may or may not be an intrinsic phosphor, to which one or more dopant(s) has been intentionally added. These dopants "activate” the phosphor and cause it to emit infrared, visible, or ultraviolet radiation. For example, in Gd2 ⁇ 2S:Tb, the Tb atoms (the dopant/activator) give rise to the optical emission of the phosphor.
• Some phosphors, such as BaFBr are known as storage phosphors. In these materials, the dopants are involved in the storage as well as the emission of radiation.
• Patent 3,778,615 (Luckey), U.S. Patent 4,032,471 (Luckey), U.S. Patent 4,225,653 (Brixner et al.), U.S. Patent 3,418,246 (Royce), U.S. Patent 3,428,247 (Yocon), U.S. Patent 3,725,704 (Buchanan et al.), U.S. Patent 2,725,704 (Swindells), U.S. Patent 3,617,743 (Rabatin), U.S. Patent 3,974,389 (Fe ⁇ i et al.), U.S. Patent 3,591,516 (Rabatin), U.S. Patent 3,607,770 (Rabatin), U.S.
• Patent 3,666,676 (Rabatin), U.S. Patent 3,795,814 (Rabatin), U.S. Patent 4,405,691 (Yale), U.S. Patent 4,311,487 (Luckey et al.), U.S. Patent 4,387,141 (Patten), U.S. Patent 5,021,327 (Bunch et al.), U.S. Patent 4,865,944 (Roberts et al.), U.S. Patent 4,994,355 (Dickerson et al), U.S. Patent 4,997,750 (Dickerson et al.), U.S. Patent 5,064,729 (Zegarski), U.S.
• Patent 5,108,881 (Dickerson et al.), U.S. Patent 5,250,366 (Nakajima et al.), U.S. Patent 5,871,892 (Dickerson et al.), EP 0 491 116A1 (Benzo et al.), cited herein with respect to the phosphors.
• Useful classes of phosphors include, but are not limited to, calcium tungstate (CaWO_t), activated or unactivated lithium stannates, niobium and/or rare earth activated or unactivated yttrium, lutetium, or gadolinium tantalates, rare earth (such as terbium, lanthanum, gadolinium, cerium, and lutetium)-activated or unactivated middle chalcogen phosphors such as rare earth oxychalcogenides and oxyhalides, and terbium-activated or unactivated lanthanum and lutetium middle chalcogen phosphors. Still other useful phosphors are those containing hafnium as described for example in U.S.
• Patent 4,988,880 (Biyan et al.), U.S. Patent 4,988,881 (Bryan et al.), U.S. Patent 4,994,205 (Biyan et al.), U.S. Patent 5,095,218 (Bryan et al.), U.S. Patent 5,112,700 (Lambert et al.), U.S. Patent
• the more prefened phosphors include alkaline earth metal fluorohalide prompt emitting and/or storage phosphors [particularly those containing iodide such as alkaline earth metal fluorobiOmoiodide storage phosphors as described in U.S. Patent 5,464,568 (Bringley et al.)].
• Another useful class of phosphors includes rare earth hosts that are rare earth activated mixed alkaline earth metal sulfates such as europium-activated barium strontium sulfate.
• one class of useful phosphors include rare earth oxychalcogenides and halide phosphors represented by the following fo ⁇ nula (1): M' (w -n)M"nO w X" d) wherein M' is at least one of the metals yttrium (Y), lanthanum (La), gadolinium
• M is at least one of the rare earth metals dysprosium (Dy), erbium (Er), europium (Eu), holmium (Ho), neodymium (Nd), praseodymium (Pr), samarium (Sm), tantalum (Ta), terbium (Tb), thulium (Tm), or ytterbium (Yb),
• X is a middle chalcogen (S, Se, or Te) or halogen
• n is 0.002 to 0.2
• w is 1 when X" is halogen or 2 when X" is a middle chalcogen.
• phosphors that are the products of firing starting materials comprising optional oxide and a combination of species characterized by the following fo ⁇ nula (2): MFX 1-z I z M a X a :yA: eQ:tD (2) wherein "M” is magnesium (Mg), calcium (Ca), strontium (Sr), or barium (Ba), "F” is fluoride, “X” is chloride (CI) or bromide (Br), "I” is iodide, M a is sodium (Na), potassium (K), rubidium (Rb), or cesium (Cs), X a is fluoride (F), chloride (CI), bromide (Br), or iodide (I), "A” is europium (Eu), cerium (Ce), samarium (Sm), or terbium (Tb), "Q” is BeO, MgO, CaO, SrO, BaO, ZnO, Al
• Still another useful class of phosphors includes phosphors that are divalent alkaline earth metal fluorohalide phosphors characterized by the following fo ⁇ nula (3): (Ba, -a . b - o Mg a Ca b Sr c )FX 1-z I z rM a X a :yA (3) wherein "M” is magnesium (Mg), calcium (Ca), strontium (Sr), or barium (Ba), "F” is fluoride, "X” is chloride (CI) or bromide (Br), "I” is iodide, M a is sodium (Na), potassium (K), mbidium (Rb), or cesium (Cs), X a is fluoride (F), chloride (CI), bromide (Br), or iodide (I), "A” is europium (Eu), cerium (Ce), samarium (Sm), or terbium (Tb), "z
• Particularly useful phosphors are those containing doped or undoped tantalum such as YTaO 4 , YTaO 4 :Nb, Y(Sr)TaO 4 , and Y(Sr)TaO :Nb. These phosphors are described in U.S. Patent 4,226,653 (Brixner), U.S. Patent 5,064,729 (Zegarski), U.S. Patent 5,250,366 (Nakajima et al.), and U.S. Patent 5,626,957 (Benso et al.). Other useful phosphors are alkaline earth metal phosphors. Storage phosphors can also be used in the practice of this invention.
• Various storage phosphors are described for example, in U.S. Patent 5,464,568 (noted above). Such phosphors include divalent alkaline earth metal fluorohalide phosphors that may optionally contain iodide. Some embodiments of these phosphors are described in more detail in U.S. Patent 5,464,568 (noted above). Still other storage phosphors are described in U.S. Patent 4,368,390 (Takahashi et al.), cited herein, and include divalent europium and other rare earth activated alkaline earth metal halides and rare earth element activated rare earth oxyhalides, as described in more detail above.
• Examples of useful phosphors include: SrS:Ce,SM, SrS:Eu,Sm, ThO 2 :Er, La 2 O 2 S:Eu,Sm, ZnS:Cu,Pb, and others described in U.S. Patent 5,227,253 (Takasu et al.).
• the one or more phosphors used in the practice of this invention are present in the photothennographic materials in an amount of at least 0.1 mole per mole, and preferably from 0.5 to 20 mole, per mole of total silver in the photothermographic material. Generally, the amount of total silver is at least 0.002 mol/m".
• the layers in which they are incoiporated (usually one or more emulsion 7 layers), have a dry coating weiglit of at least 5 g/m", and preferably from 5 g/m , to 200 g/m " .
• the one or more phosphors and the photosensitive silver halide are incorporated within the same imaging layer that has a dry coating weight within the noted prefened range.
• Binders The chemically sensitized photosensitive silver halide, the non-photosensitive source of reducible silver ions, the reducing agent composition described above, and any other imaging layer additives used in the present invention are generally combined with one or more binders that are either hydrophilic or hydrophobic.
• either aqueous or organic solvent-based fonnulations can be used to prepare the thermally developable materials of this invention.
• Mixtures of either or both types of binders can also be used. It is prefened that the binder be selected fi-om hydrophobic polymeric materials such as, for example, natural and synthetic resins that are sufficiently polar to hold the other ingredients in solution or suspension.
• hydrophobic binders include, but are not limited to, polyvinyl acetals, polyvinyl chloride, polyvinyl acetate, cellulose acetate, cellulose acetate butyrate, polyolefins, polyesters, polystyrenes, polyaciylonitrile, polycarbonates, methaciylate copolymers, maleic anhydride ester copolymers, butadiene-styrene copolymers, and other materials readily apparent to one skilled in the art. Copolymers (including terpolymers) are also included in the definition of polymers.
• polyvinyl acetals such as polyvinyl butyral and polyvinyl fo ⁇ nal
• vinyl copolymers such as polyvinyl acetate and polyvinyl chloride
• Particularly suitable binders are polyvinyl butyral resins that are available under the names BUTVAR ⁇ (Solutia, Inc.) and PIOLOFORM ® (Wacker Polymer Systems).
• Aqueous dispersions (or latexes) of hydrophobic binders may also be used either alone as binders or in combination with other binders.
• hydrophilic binders include, but are not limited to, proteins and protein derivatives, gelatin and gelatin-like derivatives (hardened or unhardened, including alkali- and acid-treated gelatins, acetylated gelatin, oxidized gelatin, phthalated gelatin, and deionized gelatin), cellulosic materials such as hydroxymethyl cellulose and cellulosic esters, acrylamide/methacrylamide polymers, acrylic/methacrylic polymers polyvinyl pynolidones, polyvinyl alcohols, poly(vinyl lactams), polymers of sulfoalkyl acrylate or methacrylates, hydrolyzed polyvinyl acetates, polyacrylamides, polysaccharides (such as dextrans and starch ethers), and other synthetic or naturally occurring vehicles commonly known for use in aqueous-based photographic emulsions (see for example, Research Disclosure, item 38957, noted above).
• cellulosic materials
• Cationic starches can be used as a peptizer for tabular silver halide grains as described in U.S. Patent 5,620,840 (Maskasky) and U.S. Patent 5,667,955 (Maskasky).
• Hardeners for various binders may be present if desired.
• Useful hardeners are well known and include diisocyanate compounds as described for example, in EP 0 600 586B1 (Philip, Jr. et al.), vinyl sulfone compounds as described in U.S. Patent 6,143,487 (Philip, Jr. et al), and EP 0 640 589A1 (Gathmann et al.), aldehydes and various other hardeners as described in U.S.
• Patent 6,190,822 (Dickerson et al.).
• the hydrophilic binders used in the photothermographic materials are generally partially or fully hardened using any conventional hardener.
• Useful hardeners are well known and are described, for example, in T. H. James, The Theoi ⁇ of the Photographic Process, Fourth Edition, Eastman Kodak Company, Rochester, NY, 1977, Chapter 2, pp. 77-78.
• the binder(s) should be able to withstand those conditions.
• a hydrophobic binder it is prefened that the binder does not decompose or lose its stmctural integrity at 120°C for 60 seconds.
• a hydrophilic binder When a hydrophilic binder is used, it is prefened that the binder does not decompose or lose its stmctural integrity at 150°C for 60 seconds. It is more prefened that it does not decompose or lose its stmctural integrity at 177°C for 60 seconds.
• the polymer binder(s) is used in an amount sufficient to carry the components dispersed therein.
• the effective range of the amount of polymer can be appropriately determined by one skilled in the art.
• a binder is used at a level of 10% by weight to 90% by weight, and more preferably at a level of 20% by weight to 70% by weight, based on the total diy weight of the layer in which it is included.
• the amount of binders in double-sided photothemiographic materials may be the same or different. It is particularly useful in the photothermographic materials of this invention to use predominantly (more than 50% by weight of total binder weight) hydrophobic binders in both imaging and non-imaging layers on both sides of the support.
• the hydrophobic binder is mixed into the photothermographic emulsion prepared according to this invention to fonn a photothermographic emulsion formulation for coating onto a support.
• the photothemiogi-aphic materials of this invention comprise a polymeric support that is preferably a flexible, transparent film that has any desired thickness and is composed of one or more polymeric materials, depending upon their use.
• the supports are generally transparent (especially if the material is used as a photomask) or at least translucent, but in some instances, opaque supports may be useful. They are required to exhibit dimensional stability during thermal development and to have suitable adhesive properties with overlying layers.
• Useful polymeric materials for making such supports include, but are not limited to, polyesters (such as polyethylene terephthalate and polyethylene naphthalate), cellulose acetate and other cellulose esters, polyvinyl acetal, polyolefins (such as polyethylene and polypropylene), polycarbonates, and polystyrenes (and polymers of styrene derivatives).
• Prefened supports are composed of polymers having good heat stability, such as polyesters and polycarbonates.
• Polyethylene terephthalate film is a particularly prefened support.
• Various support materials are described, for example, in Research Disclosure, August 1979, item 18431. A method of making dimensionally stable polyester films is described in Research Disclosure, September 1999, item 42536.
• Support materials may also be treated or annealed to reduce shrinkage and promote dimensional stability. It is also useful to use supports comprising dichroic minor layers wherein the dichroic minor layer reflects radiation at least having the predetermined range of wavelengths to the emulsion layer and transmits radiation that has wavelengths outside the predetermined range of wavelengths. Such dichroic supports are described in U.S. Patent 5,795,708 (Boutet). It is further useful to use transparent, multilayer, polymeric supports comprising numerous alternating layers of at least two different polymeric materials. Such multilayer polymeric supports preferably reflect at least 50%) of actinic radiation in the range of wavelengths to winch the photothermographic material is sensitive, and provide photothennographic materials having increased speed.
• Opaque supports can also be used, such as dyed polymeric films and resin-coated papers that are stable to high temperatures.
• Support materials can contain various colorants, pigments, antihalation or acutance dyes if desired.
• blue-tinted supports are particularly useful for providing images useful for medical diagnosis.
• Support materials may be treated using conventional procedures (such as corona discharge) to improve adhesion of overlying layers, or subbing or other adhesion-promoting layers can be used.
• Useful subbing layer formulations include those conventionally used for photographic materials such as vinylidene halide polymers.
• Photothermographic Formulations The present invention also provides a method for preparing photothemiographic materials.
• This method includes the steps (A) through (D), and optionally step (E) described above in relation to the method of making a photothennographic emulsion (and in the various orders noted above).
• preparing the photothe ⁇ nogi-aphic material involves at least steps (A) through (D), followed by: (E') simultaneously with any of steps (B) through (D), or subsequently to step (D), adding a binder to fonn an emulsion formulation, and (F) after step (E'), coating and diying the emulsion fonnulation on a support to provide a photothemiographic imaging material.
• a reducing agent composition can also be added to the photothermographic emulsion at any suitable point.
• step (E) can be used wherein some of the reducible silver ions in the non-photosensitive source of reducible silver ions are converted into photosensitive silver halide grains by addition of an inorganic or an organic halide (such as lithium bromide, calcium bromide, or zinc bromide).
• the steps are ca ⁇ ied out in the order of step (A), step (B), step (C), step (D), step (E), step (E'), and step (F).
• the method steps can be canned out in the order of step (A), step (B), step (D), step (C), step (E"), and step (F), or in the order of step (A), step (D), step (B), step (C), step (E'), and step (F).
• An organic solvent-based coating fo ⁇ nulation for the photothermo- graphic emulsion layer(s) can be prepared by mixing the photothermographic emulsion prepared according to the present invention with one or more binders, the reducing composition, toner(s), and optional addenda in a suitable solvent system that usually includes an organic solvent, such as toluene, 2-butanone (methyl ethyl ketone), acetone, or tetrahydrofuran, or mixtures thereof.
• the desired imaging components can be fonnulated with a hydrophilic binder (such as gelatin, a gelatin-derivative, or a latex) in water or water-organic solvent mixtures to provide aqueous-based coating fonnulations.
• Photothennographic materials of the invention can contain plasticizers and lubricants such as poly( alcohols) and diols of the type described in U.S. Patent 2,960,404 (Milton et al.), fatty acids or esters such as those described in U.S. Patent 2,588,765 (Robijns) and U.S. Patent 3,121,060 (Duane), and silicone resins such as those described in GB 955,061 (DuPont).
• the materials can also contain matting agents such as starch, titanium dioxide, zinc oxide, silica, and polymeric beads including beads of the type described in U.S. Patent 2,992,101 (Jelley et al.) and U.S. Patent 2,701,245 (Lynn).
• Polymeric fluorinated surfactants may also be useful in one or more layers of the imaging materials for various purposes, such as improving coatability and optical density uniformity as described in U.S. Patent 5,468,603 (Kub).
• U.S. Patent 6,436,616 (Geisler et al.) describes various means of modifying photothemiographic materials to reduce what is known as the "woodgrain" effect, or uneven optical density. This effect can be reduced or eliminated by several means, including treatment of the support, adding matting agents to the topcoat, using acutance dyes in certain layers or other procedures described in the noted publication.
• the photothe ⁇ nogi-aphic materials of this invention can include one or more antistatic agents in any of the layers including the photothermographic emulsion layer, or in separate conductive layers, on either or both sides of the support.
• conductive components include, but are not limited to, soluble salts (for example, chlorides or nitrates), evaporated metal layers, or ionic polymers such as those described in U.S. Patent 2,861,056 (Minsk) and U.S. Patent 3,206,312 (Stennan et al.), or insoluble inorganic salts such as those described in U.S. Patent 3,428,451 (Trevoy), electroconductive underlayers such as those described in U.S.
• Patent 5,310,640 Markin et al
• electronically- conductive metal antimonate particles such as those described in U.S. Patent 5,368,995 (Christian et al)
• electrically-conductive metal-containing particles dispersed in a polymeric binder such as those described in EP 0 678 776 Al
• conductive particles are the non-acicular metal antimonate particles described in copending and commonly assigned U.S. Serial No. 10/304,224 (filed on November 27, 2002 by LaBelle, Sakizadeh, Ludemann, Bhave, and Pham).
• Other antistatic agents are well known in the art.
• Still other conductive compositions include one or more fluoro- chemicals each of which is a reaction product of R f -CH 2 CH 2 -SO 3 H with an amine wherein R f comprises 4 or more fully fluorinated carbon atoms. These antistatic compositions are described in more detail in U.S. Published Application 2003-0198901 (Sakizadeh et al.).
• Additional conductive compositions include one or more fluoro- chemicals having the stmcture R f -R-N(R' ⁇ )(R' 2 )(R' 3 .) + X " wherein Rf is a straight or branched chain perfluoroalkyl group having 4 to 18 carbon atoms, R is a divalent linking group comprising at least 4 carbon atoms and a sulfide group in the chain, R" ⁇ , R" 2 , R' 3 are independently hydrogen or alkyl groups or any two of R' ⁇ , R' 2 , and R' 3 taken together can represent the carbon and nitrogen atoms necessary to provide a 5- to 7-membered heterocyclic ring with the cationic nitrogen atom, and X " is a monovalent anion.
• the photothermographic materials of this invention can be constmcted of one or more layers on the imaging side of the support.
• Single layer materials should contain the chemically sensitized silver halide, the non-photosensitive source of reducible silver ions, the reducing agent composition, the binder, as well as optional materials such as toners, acutance dyes, coating aids, and other adjuvants.
• Two-layer constructions comprising a single imaging layer coating containing all the ingredients and a surface protective topcoat are generally found on the frontside of the materials of this invention.
• each side of the support can include one or more of the same or different imaging layers, interlayers, and protective topcoat layers. In such materials preferably a topcoat is present as the outermost layer on both sides of the support.
• the thermally developable layers on opposite sides can have the same or different construction and can be overcoated with the same or different protective layers.
• the polycarboxylic acid compound(s) can be the same or different on opposite sides of the support.
• Layers to promote adhesion of one layer to another in photothennographic materials are also known, as described for example in U.S. Patent 5,891,610 (Bauer et al), U.S. Patent 5,804,365 (Bauer et al.), and U.S. Patent 4,741,992 (Przezdziecki). Adhesion can also be promoted using specific polymeric adhesive materials as described for example in U.S. Patent 5,928,857 (Geisler et al). Layers to reduce emissions from the film may also be present, including the polymeric ba ⁇ ier layers described in U.S. Patent 6,352,819 (Kenney et al.), U.S. Patent 6,352,820 (Bauer et al), U.S.
• Patent 6,420,102 (Bauer et al.), and in copending and commonly assigned U.S. Patent 6,667,148 (Rao et al.), and U.S. Patent 6,746,831 (Hunt).
• Photothemiographic formulations described herein can be coated by various coating procedures including wire wound rod coating, dip coating, air knife coating, curtain coating, slide coating, or extrusion coating using hoppers of the type described in U.S. Patent 2,681,294 (Beguin). Layers can be coated one at a time, or two or more layers can be coated simultaneously by the procedures described in U.S. Patent 2,761,791 (Russell), U.S. Patent 4,001,024 (Dittman et al), U.S.
• Patent 4,569,863 (Keopke et al.), U.S. Patent 5,340,613 (Hanzalik et al.), U.S. Patent 5,405,740 (LaBelle), U.S. Patent 5,415,993 (Hanzalik et al.), U.S. Patent 5,525,376 (Leonard), U.S. Patent 5,733,608 (Kessel et al.), U.S. Patent 5,849,363 (Yapel et al.), U.S. Patent 5,843,530 (Jerry et al.), U.S. Patent 5,861,195 (Bhave et al.), and GB 837,095 (llford).
• a typical coating gap for the emulsion layer can be fi-om 10 to 750 ⁇ m, and the layer can be dried in forced air at a temperature of from 20°C to 100°C. It is prefened that the thickness of the layer be selected to provide maximum image densities greater than 0.2, and more preferably, fi-om 0.5 to 5.0 or more, as measured by a MacBeth Color Densitometer Model TD 504.
• a protective overcoat fo ⁇ nulation can be applied over the emulsion formulation.
• the two formulations are applied simultaneously.
• a "canier" layer formulation comprising a single-phase mixture of the two or more polymers described above may be applied directly onto the support and thereby located underneath the emulsion layer(s).
• Such fomiulations are described in U.S. Patent 6,355,405 (Ludemann et al.).
• the canier layer formulation is applied to the support simultaneously with application of the photothermographic emulsion layer formulation. Mottle and other surface anomalies can be reduced in the photothermographic materials of this invention by incorporation of a fluorinated polymer as described for example in U.S. Patent 5,532,121 (Yonkoski et al.) or by using particular drying techniques as described, for example in U.S.
• Patent 5,621,983 (Ludemann et al).
• two or more layer fo ⁇ nulations are applied to a film support using slide coating.
• the first layer can be coated on top of the second layer while the second layer is still wet.
• the first and second fluids used to coat these layers can be the same or different solvents (or solvent mixtures).
• manufacturing methods can also include fonning on the opposing or backside of the polymeric support, one or more additional layers, including a conductive layer, an antihalation layer, or a layer containing a matting agent (such as silica), or a combination of such layers.
• one backside layer can perform all of the desired functions.
• the photothemiographic materials of this invention can include photothermographic emulsion layers on both sides of the support and/or at least one infrared radiation absorbing heat-bleachable composition as an antihalation underlayer beneath at least one emulsion layer.
• Photothermographic materials having thermally developable layers disposed on both sides of the support often suffer from "crossover.” Crossover results when radiation used to image one side of the photothe ⁇ nogi-aphic material is transmitted through the support and images the photothe ⁇ nogi-aphic layers on the opposite side of the support. Such radiation causes a lowering of image quality (especially sharpness). As crossover is reduced, the shaiper becomes the image.
• Various methods are available for reducing crossover. Such
• anti-crossover materials can be materials specifically included for reducing crossover or they can be acutance or antihalation dyes. In either situation, when imaged with visible radiation, it is often necerney that they be rendered colorless during processing.
• photothermographic materials prepared by the present invention can contain one or more layers containing acutance and/or antihalation dyes. These dyes are chosen to have absorption close to the exposure wavelength and are designed to absorb scattered light.
• One or more antihalation compositions may be incoiporated into one or more antihalation layers according to known techniques, as an antihalation backing layer, as an antihalation underlayer, or as an antihalation overcoat.
• one or more acutance dyes may be incoiporated into one or more frontside layers such as the photothemiographic emulsion layer, primer layer, underlayer, or topcoat layer according to known techniques. It is prefened that the photothe ⁇ nogi-aphic materials of this invention contain an antihalation composition on the backside of the support, and more preferably in the backside conductive layer. Dyes useful as antihalation, filter, crossover prevention (anti-crossover), anti-i ⁇ adiation and/or acutance dyes include squaraine dyes described in U.S. Patent 5,380,635 (Gomez et al.), U.S. Patent 6,063,560 (Suzuki et al.), U.S.
• Patent 6,432,340 (Tanaka et al.), U.S. Patent 6,444,415 (Tanaka et al.), and EP 1 083 459 Al (Kimura), the indolenine dyes described in EP 0 342 810 Al (Leichter), and the cyanine dyes described in U.S. Published Application 2003-0162134 (Hunt et al.). It is also useful to employ compositions including acutance or antihalation dyes that will decolorize or bleach with heat during processing. Dyes and constmctions employing these types of dyes are described in, for example, U.S. Patent 5,135,842 (Kitchin et al.), U.S.
• Patent 5,266,452 (Kitchin et al.), U.S. Patent 5,314,795 (Helland et al.), U.S. Patent 6,306,566B2, (Sakurada et al.), U.S. Published Application 2001-0001704 (Sakurada et al.), JP Kokai 2001-142175 (Hanyu et al), and JP Kokai 2001-183770 (Hanye et al.).
• Also useful are bleaching compositions described in JP Kokai 11-302550 (Fujiwara), JP Kokai 2001-109101 (Adachi), JP Kokai 2001-51371 (Yabuki et al.), and JP
• Particularly useful heat-bleachable backside antihalation compositions can include an infrared radiation absorbing compound such as an oxonol dyes and various other compounds used in combination with a hexaarylbiimidazole (also known as a "HABI"), or mixtures thereof.
• HABI compounds are well known in the art, such as U.S. Patent 4,196,002 (Levinson et al.), U.S. Patent 5,652,091 (Peny et al.), and U.S. Patent 5,672,562 (Perry et al.).
• Patent 6,558,880 (Goswami et al.). Under practical conditions of use, the compositions are heated to provide bleaching at a temperature of at least 90°C for at least 0.5 seconds.
• the photothe ⁇ nogi-aphic materials of this invention include a surface protective layer over one or more imaging layers one both sides of the support.
• the photothermographic materials include a surface protective layer on the same side of the support as the one or more photothennographic emulsion layers and a layer on the backside that includes an antihalation composition and/or conductive antistatic components. A separate backside surface protective layer can also be included in these embodiments.
• the photothennographic materials of the present invention can be imaged in any suitable manner consistent with the type of material by using any suitable imaging source (typically some type of radiation or electronic signal).
• the materials are sensitive to radiation in the range of from at least 300 mn to 1400 nm, and preferably fi-om 300 nm to 850 mn.
• Imaging can be achieved by exposing the photothennographic materials of this invention to a suitable source of radiation to which they are sensitive, including ultraviolet radiation, visible light, near infrared radiation, and infrared radiation to provide a latent image.
• Suitable exposure means are well known and include sources of radiation, including: incandescent or fluorescent lamps, xenon flash lamps, lasers, laser diodes, light emitting diodes, infrared lasers, infrared laser diodes, infrared light-emitting diodes, infrared lamps, or any other ultraviolet, visible, or infrared radiation source readily apparent to one skilled in the art, and others described in the art, such as in Research Disclosure, September, 1996, item 38957.
• Particularly useful infrared exposure means include laser diodes, including laser diodes that are modulated to increase imaging efficiency using what is known as multi-longitudinal exposure techniques as described in U.S. Patent 5,780,207 (Mohapatra et al.).
• the photothermographic materials of the present invention can be imaged using any suitable X-radiation imaging source to provide a latent image.
• suitable exposure means are well known and include medical, mammography, dental, and industrial X-ray units. The ⁇ nal development conditions will vaiy, depending on the construction used but will typically involve heating the imagewise exposed material at a suitably elevated temperature.
• the latent image can be developed by heating the exposed material at a moderately elevated temperature of, for example, from 50°C to 250°C (preferably from 80°C to 200°C and more preferably from 100°C to 200°C) for a sufficient period of time, generally fi-om 1 to 120 seconds. Heating can be accomplished using any suitable heating means such as a hot plate, a steam iron, a hot roller or a heating bath.
• a prefened heat development procedure includes heating at from 110°C to 135°C for fi-om 3 to 25 seconds. In some methods, the development is canied out in two steps.
• Themial development takes place at a higher temperature for a shorter time (for example at 150°C for up to 10 seconds), followed by thermal diffusion at a lower temperature (for example at 80°C) in the presence of a transfer solvent.
• thermal development can take place using a preheating step (for example at 110°C for up to 10 seconds), immediately followed by a final development step (for example at 125°C for up to 20 seconds).
• the photothe ⁇ nogi-aphic materials of the present invention are sufficiently transmissive in the range of from 350 to 450 nm in non-imaged areas to allow their use in a method where there is a subsequent exposure of an ultraviolet or short wavelength visible radiation sensitive imageable medium. For example, imaging the materials and subsequent development affords a visible image.
• the heat-developed photothermographic materials absorb ultraviolet or short wavelength visible radiation in the areas where there is a visible image and transmit ultraviolet or short wavelength visible radiation where there is no visible image.
• the heat-developed materials may then be used as a mask and positioned between a source of imaging radiation (such as an ultraviolet or short wavelength visible radiation energy source) and an imageable material that is sensitive to such imaging radiation, such as a photopolymer, diazo material, photoresist, or photosensitive printing plate. Exposing the imageable material to the imaging radiation through the visible image in the exposed and heat-developed photo- themiographic material provides an image in the imageable material. This method is particularly useful where the imageable medium comprises a printing plate and the photothennographic material serves as an imagesetting film.
• a source of imaging radiation such as an ultraviolet or short wavelength visible radiation energy source
• an imageable material that is sensitive to such imaging radiation such as a photopolymer, diazo material, photoresist, or photosensitive printing plate.
• a method for the fomiation of a visible image comprises: A) imagewise exposing the photothe ⁇ nogi-aphic material of this invention to electromagnetic radiation to which the chemically sensitized silver halide is sensitive, to form a latent image, and B) simultaneously or sequentially, heating the exposed material to develop the latent image into a visible image.
• the photothemiographic material may be exposed in step A using any source of radiation, to which it is sensitive, including: ultraviolet radiation, visible light, infrared radiation or any other infrared radiation source readily apparent to one skilled in the art.
• This visible image prepared fi-om a photothennographic material can also be used as a mask for exposure of other photosensitive imageable materials, such as graphic arts films, proofing films, printing plates and circuit board films, that are sensitive to suitable imaging radiation (for example, UV radiation).
• imaging an imageable material such as a photopolymer, a diazo material, a photoresist, or a photosensitive printing plate
• an imageable material such as a photopolymer, a diazo material, a photoresist, or a photosensitive printing plate
• the image-fo ⁇ ning method further comprises: C) positioning the exposed and heat-developed photothermographic material between a source of imaging radiation and an imageable material that is sensitive to the imaging radiation, and D) exposing the imageable material to the imaging radiation through the visible image in the exposed and heat-developed photothennographic material to provide an image in the imageable material.
• the photothermographic materials described herein are also useful in an imaging assembly comprising one or more phosphor intensifying screens adjacent the front and/or back of the photothe ⁇ nogi-aphic material.
• Such screens are well known in the art [for example, U.S. Patent 4,865,944 (Roberts et al.) and U.S. Patent 5,021,327 (Bunch et al.)].
• An assembly (often known as a cassette), can be prepared by ananging the photothennographic material, and the one or more screens in a suitable holder and appropriately packaging them for transport and imaging uses.
• the phosphor intensifying screen can be positioned in
• Double-coated X-radiation sensitive photothermographic materials that is, materials having one or more thermally developable imaging layers on both sides of the support
• the front and back screens can be appropriately chosen depending upon the type of emissions desired, the desired photicity, emulsion speeds, and percent crossover.
• a metal (such as copper or lead) screen can also be included if desired.
• Constmctions and imaging assemblies useful in industrial radiography include, for example, U.S. Patent 4,480,024 (Lyons et al), U.S. Patent 5,900,357 (Feumi- Jantou et al), and EP 1 350 883 Al (Pesce et al.).
• the following examples are provided to illustrate the practice of the present invention and the invention is not meant to be limited thereby.
• ACRYLOID ® A-21 is an acrylic copolymer available from Rohm and Haas (Philadelphia, PA).
• BUTVAR " B-79 is a polyvinyl butyral resin available from Solutia, Inc. (St. Louis, MO).
• CAB 171-15S is a cellulose acetate butyrate resin available fi-om Eastman Chemical Co. (Kingsport, TN).
• DESMODURTM N3300 is an aliphatic hexamethylene diisocyanate that is available fi-om Bayer Chemicals (Pittsburgh, PA).
• Diphenylphosphine sulfide (DPPS) was obtained from Organometallics, Inc (East Hampstead, NH)
• PIOLOFORM ® BM-18 and PIOLOFORM ® BL-16 are polyvinyl butyral resins available from Wacker Polymer Systems (Adrian, MI).
• MEK is methyl ethyl ketone (or 2-butanone).
• PHP is pyridinium hydrobromide perbromide.
• the Fischer X-Ray machine was a Model 36600G and was obtained fi-om Fischer Imaging Corporation (Denver, CO).
• the X-Rite ® Model 301 densitometer was obtained from X-Rite Inc. (Grandville, MI).
• Vinyl Sulfone-1 (VS-1) is described in U.S. Patent 6,143,487 and is believed to have the stmcture shown below.
• Antifoggant-A is tribiOmomethylsulfonylpyridine. It is believed to have the stmcture shown below.
• Ethyl-2-cyano-3-oxobutanoate (Antifoggant-B) is described in U.S. Patent 5,686,228 and is believed to have the stmcture shown below.
• Backcoat Dye BC-1 is cyclobutenediylium, l,3-bis[2,3-dihydro- 2,2-bis[[l-oxohexyl)oxy]methyl]-lH-perimidin-4-yl]-2,4-dihydroxy-, bis(inner salt). It is believed to have the stmcture shown below.
• Compound S-1 is a sulfur-containing chemical sensitizing dye and is believed to have the structure shown below.
• Comparative Compound C-1 is described in JP Kokai 2002-250984 (Kimura) and is believed to have the stmcture shown below.
• a stined mixture of diphenylphosphine sulfide (1.09 g, 0.005 mol) and 2-chloiO-4'-fluoropiOpiophenone (Matrix Scientific, Columbia, SC) (1.03 g, 0.0055 mol) in methylene chloride (25 ml) were cooled to 0°C. While stirring under nitrogen blanket, powdered potassium hydroxide (0.98 g, 0.0175 mol) was added at once. Cooling was removed, the reaction was allowed to warm to room temperature, and stining was continued. The mixture turned cloudy after 30 minutes. Stining was continued for 16 hours during which time the color of reaction turned orange.
• Example 1 Use in Photothermographic Materials
• a prefonned silver bromide, silver carboxylate "soap" dispersion was prepared as described in U.S. Patent 6,413,710 (Shor et al.). The average grain size was 0.14 ⁇ m.
• Photothennographic Emulsion Formulation Chemically sensitized photothemiographic emulsions were prepared according to procedures described in U.S. Patent 6,423,481 (Simpson et al.) but incoiporating the sulfur-containing compounds of this invention and using the materials and amounts shown below. The materials were added 10 to 60 minutes apart and the temperature during addition ranged from 50°F to 70°F
• a protective topcoat for the photothemiographic emulsion layer was prepared as follows: ACRYLOID ® A-21 0.58 g CAB 1 71-15S 14.9 g MEK 200 g VS-1 0.3 g Benzotriazole 1.6 g Antifoggant-A 0.24 g Antifoggant-B 0.12 g
• the photothennographic emulsion and topcoat formulations were coated under safelight conditions using a dual knife coating machine onto a 7 mil (178 ⁇ m) blue-tinted polyethylene terephthalate support provided with a backside antihalation layer containing Dye BC-1 in CAB 171-15S resin binder. Samples were dried for 7 minutes at 87°C.
• the silver coating weights were approximately 2.2 to 2.3 g/m 2 .
• Samples of the photothermographic materials were imagewise exposed for 10 "3 seconds using an EG&G Flash sensitometer equipped with both a P-16 filter and a 0.7 neutral density filter to provide continuous tone "wedges.” Following exposure, the films were developed using a heated roll processor for 15 seconds at 122.2°C to 122.8°C. Densitometiy measurements were made on a custom built computer-scanned densitometer and meeting ISO Standards 5-2 and 5-3. They are believed to be comparable to measurements fi-om commercially available densitometers.
• Density of the wedges was then measured with a computer densitometer using a filter appropriate to the sensitivity of the photothe ⁇ nogi-aphic material to obtain graphs of density versus log exposure (that is, D log E cuives).
• Emulsion formulations were made with compounds PS-1, PS-2, PS-3, and PS-4. Comparative formulations were also prepared. The sensitometric results, shown below in TABLE I demonstrate the increase in speed when the PS compounds of this invention are formulated along with gold(III) compounds. Only a small increase in Dmin was found.
• Example 2 Use in Phosphor-Containing Photothermographic Materials
• YSrTaO 4 phosphor having an average size of 4.0 ⁇ m.
• the materials were mixed for 15 minutes to prepare the final photothennographic coating formulations.
• Photothe ⁇ nogi-aphic materials were coated and dried as described in Example 1.
• the approximate phosphor coating weights were fi-om 79 to 82 g/m".
• the photothermographic materials were imaged, developed, and evaluated as described above in Example 1.
• the X-ray sensitometric response of these photothermographic materials was determined by exposing the samples using a Fischer X-ray unit operating at 200 mA and 76 KeV and filtered with a 3.0 mm sheet of aluminum. The samples were placed on a table set at 85.5 cm from the X-ray source. A series of X-ray exposures of constant intensity and exposure times from 0.1 sec to 1.5 sec were made. Exposed samples were developed in a manner similar to that described in Example 1. The density of these samples were measured with a X-Rite ® 310 densitometer using the Status A filters and measured with the visible filter.
• Example 3 Use in Phosphor-Containing High-Contrast Photothermographic Materials
• Photothermographic materials were prepared, imaged and developed as described in Example 2 except that to 25 g of each of the photothermographic emulsions was also added 0.4 ml of a solution prepared by dissolving 0.43 g of high-contrast agent, compound CN-08, in 7.4 g of methanol.
• the sensitometric results shown below in TABLE IN, demonstrate the increase in speed when the (PS) compounds of this invention are fonnulated along with gold(III) compounds in a phosphor-containing high-contrast photothe ⁇ nogi-aphic material.
• the sensitometric X-ray response was also measured as described in Example 2.
• the sensitometric response after X-ray exposure shown below in TABLE V demonstrates that significant X-ray sensitivity was obtained by addition of the chemical sensitizer (PS) compounds of this invention in combination with gold(III) sensitized emulsions containing the high-contrast agent, CN-08.
• PS chemical sensitizer
• TABLE V also shows the materials had good differentiation between developed density and Dmin.
• D logE curves showed low Dmin, and good speed and contrast.
• Examples 4-7 demonstrate the use of the PS compounds in photothemiographic emulsions having a silver halide with an average grain size of 0.20 ⁇ m.
• Example 4 Use in Photothermographic Materials The preparation of a photothermographic formulation was canied out as follows: A prefonned silver bromide, silver carboxylate "soap" dispersion was prepared as described in U.S. Patent 6,413,710 (Shor et al.). The average grain size was 0.20 ⁇ m. Chemically sensitized photothemiographic emulsions were prepared according to procedures described in U.S. Patent 6,423,481 (Simpson et al.) but incoiporating the PS compounds of this invention and using the materials and amounts as described in Example 1. Emulsion fonnulations were made with compounds PS-1 and PS-4. Comparative formulations were also prepared.
• Example 5 Use in Phosphor-Containing Photothermographic Materials To 25 g aliquots of each of the photothennographic emulsion fonnulations prepared above in Example 4, was added 18.2 g of YSrTaO phosphor having an average size of 4.0 ⁇ m. The materials were mixed for 5 minutes to prepare the final photothennographic coating fonnulations.
• Comparative fonnulations were also prepared. Photothermographic materials were coated and dried as described in Example 1. The approximate phosphor coating weights were fi-om 78 to 82 g/m 2 . The photothemiographic materials were imaged, developed, and evaluated as described above in Example 1. The sensitometric results, shown below in TABLE VII, demonstrate the increase in speed when the (PS) compounds of this invention are fomiulated along with gold(III) compounds in a phosphor- containing photothe ⁇ nogi-aphic material.
• the X-ray sensitometric response of these photothennographic materials was determined by exposing the samples using a Fischer X-ray unit operating at 200 mA and 76 KeV filtered with a 3.0 mm sheet of aluminum. The samples were placed on a table set at 85.5 cm fi-om the X-ray source. A series of X-ray exposures of constant intensity and exposure times of from 0.1 sec to 1.5 sec was made. After samples were exposed they were processed in a manner similar as described in Example 1. The density of these samples were measured with a X-Rite ® 310 densitometer using the Status A filters and measured with the visible filter.
• TABLE VIII The sensitometric results, shown below in TABLE VIII, demonstrate the increase in sensitivity to X-rays when the (PS) compounds of this invention are fonnulated along with gold(III) compounds in a phosphor-containing photothennographic material. TABLE VIII also shows the materials had good differentiation between developed density and Dmin. In addition, D log E curves showed low Dmin, and good speed and contrast.
• Example 6 - Use in Photothermographic Materials A comparison of photothe ⁇ nogi-aphic materials incorporating compound PS-1 and Au-2 with compound S-1, a known sulfur sensitizer described in U.S. Patent 5,891,615 (Winslow et al.) and Au-2 is shown below. Photothennographic emulsions were prepared, as described in
• Example 1 except that 7.9 ml of PS-1 solution and 1.48 g of Antifoggant-A in 16.72 g of MEK was used in the photothermographic emulsion formulation, and no Antifoggant A was added to the topcoat formulation.
• the sample containing compound S-1 was prepared by adding a solution containing 0.02 g of compound S-1 in 2.5 g of methanol and 2.5 g of
• Example 7 Use in Phosphor-Containing Photothermographic Materials
• YSrTaO phosphor having an average size of 0.4 ⁇ m.
• the materials were mixed for 15 minutes to prepare the final photothermographic coating formulations. Comparative formulations were also prepared.
• Photothermographic materials were coated and dried as described in Example 1. The approximate phosphor coating weights were from 76 to 81 g/m .
• the photothermographic materials were imaged, developed, and evaluated as described above in Example 1.
• the sensitometric results, shown below in TABLE XI demonstrate that both constmctions have similar photospeeds. However, the sample containing compound PS-1 had both lower Dmin and higher contrast than the sample containing compound S-1, even though compound PS-1 was present at 2.5 molar equivalents to compound S-1.
• the X-ray sensitometric response of these photothennographic materials was dete ⁇ nined by exposing the samples using a Fischer X-ray unit operating at 200 mA and 76 KeV and filtered with a 3.0 mm sheet of aluminum.
• the samples were placed on a table set at 85.5 cm from the X-ray source.
• a series of X-ray exposures of constant intensity and exposure times of fi-om 0.1 sec to 1.5 sec was made.
• Exposed samples were processed in a manner similar to that described in Example 1.
• the density of these samples were measured with a X-Rite ® 310 densitometer using the Status A filters and measured with the visible filter.
• Example 8 This example compares photothermographic materials incoiporating known chemical sensitizing compound C-1 used in combination with compound Au-2 with compound PS-1 used in combination with compound Au-2. Photothermographic materials were prepared, imaged and developed as described in Example 1 except that 7.9 ml of a solution of 1.53 x 10 "4 moles of compound PS-1 in 8.64 g of a 1 :1 mixture of MEK MeOH and 1.77 g of Antifoggant-A in 10.00 g of MEK was used in the photothennographic emulsion fonnulation, and no Antifoggant-A was added to the topcoat formulation.
• Example 9 Use in Phosphor-Containing Photothermographic Materials
• the X-ray sensitometric response of these photothermographic materials was determined by exposing the samples using a Fischer X-ray unit operating at 200 mA and 76 KeN and filtered with a 3.0 mm sheet of aluminum. The samples were placed on a table set 85.5 cm from the X-ray source. A series of X-ray exposures of constant intensity and exposure times from 0.1 sec to 1.5 sec were made. Exposed samples were developed in a manner similar to that described in Example 1. The density of these samples were measured with a X-Rite ® 310 densitometer using the Status A filters and measured with the visible filter.
• Example 10 Use in Photothermographic Materials
• Photothermographic emulsions were prepared, as described in Example 1 except that 7.9 ml of PS-1 solution, 12 g of PIOLOFORM ® BM-18 and 8 g of PIOLOFORM ® BL-16 were used instead of 20 g of BUTNAR ® B-79, and 1.48 g of Antifoggant-A in 16.72 g of MEK were used in the photothermographic emulsion formulation, and Antifoggant-A was not added to the topcoat fo ⁇ nulation.
• the sample containing compound S-1 was prepared by adding a solution containing 0.02 g of compound S-1 in 2.5 g of methanol and 2.5 g of MEK in place of compound PS-1. Samples were coated, dried, imaged, and developed as described in
• Example 1 The silver coating weights were from 2.28 to 2.30 g/m 2 .
• the sample containing compound PS-1 had lower Dmin than the sample containing compound S-1, even though compound PS-1 was present at 2.5 molar equivalents to compound S-1.
• Example 11 Use in Photothermographic Materials
• Photothermographic emulsions were prepared, as described in Example 1 except that 7.9 ml of PS-1 was added to the photothermographic emulsion formulation, and 12.0 g of PIOLOFORM ® BM-18 and 8 g of PIOLOFORM ® BL-16 were used instead of BUTVAR ® B-79, and Antifoggant-A was not added to the topcoat formulation.
• the sample containing compound S-1 was prepared by adding a solution containing 0.02 g of compound S-1 in 2.5 g of methanol and 2.5 g of MEK in place of compound PS-1. Samples were coated, dried, imaged, and developed as described in Example 1. The silver coating weights were from 2.25 to 2.29 g/m 2 .
• Example 12 Use in Phosphor-Containing Photothermographic Materials To 25 g aliquots of each of the photothermographic emulsion formulations prepared above in Example 11 except that Antifoggant-A was added to the topcoat, was added 18.2 g of YSrTaO 4 phosphor having an average size of 4.0 ⁇ m. The materials were mixed for 15 minutes to prepare the final photo- themiographic coating formulations. Comparative formulations were also prepared. Photothermographic materials were coated and dried as described in Example 1. The approximate phosphor coating weights were at 81 g/m 2 . The photothermographic materials were imaged, developed, and evaluated as described above in Example 1.
• the X-ray sensitometric response of these photothemiographic materials was determined by exposing the samples using a Fischer X-ray unit operating at 200 lnA and 76 KeV and filtered with a 3.0 mm sheet of aluminum. The samples were placed on a table set 85.5 cm fi-om the X-ray source. A series of X-ray exposures of constant intensity and exposure times of from 0.1 sec to 1.5 sec was made. Exposed samples were processed in a manner similar to that described in Example 1. The density of these samples were measured with a X-Rite " 310 densitometer using the Status A filters and measured with the visible filter. The sensitometric results, shown below in TABLE XXIII, demonstrate that both samples were sensitive to X-radiation.
• Example 13 Use in Photothermographic Materials The preparation of a photothermographic formulation was canied out as follows: A prefonned silver bromide, silver carboxylate "soap" was prepared as described in U.S. Patent 6,413,710 (Shor et al.). The average grain size was 0.15 ⁇ m.
• Photothermographic Emulsion Fo ⁇ nulation Chemically sensitized photothermographic emulsions were prepared according to procedures described in U.S. Patent 6,423,481 (Simpson et al.) but incoiporating the sulfur-containing compounds of this invention and using the materials and amounts as described below. The materials were added 10 to 60 minutes apart and the temperature during addition ranged from 50°F to 70°F
• a protective topcoat for the photothe ⁇ nogi-aphic emulsion layer was prepared as follows: ACRYLOID ⁇ A-21 0.58 g CAB 171-15S 14.9 g MEK 200 g VS-1 0.3 g Benzotriazole 1.6 g Antifoggant-A 0.24 g Antifoggant-B 0.12 g
• the photothermographic fonnulations were coated, dried, imaged, and developed as described in Example 1. Emulsion formulations were made with compounds PS-1.
• the sensitometric results, also shown below in TABLE XXIV demonstrate the effects on Dmin, speed, and contrast by the addition of ZnBr 2 before or after the addition of PS-1 compound, or after the PHP oxidizing compound. Higher contrast is observed when ZnBr? is added before the PHP but after compound PS-1. The fastest speed is observed when ZnBr? is added before compound PS-1.
• Example ZnBr 2 added ZnBr 2 added ZnBr 2 Dmin SP-2 AC-1 AC-2 Before PS-1 After PS-1 added After PHP
• Example 14 Use in Phosphor-Containing Photothermographic Materials
• YSrTaO 4 phosphor having an average size of 4.0 ⁇ m.
• the materials were mixed for 5 minutes to prepare the final photothe ⁇ nogi-aphic coating fonnulations.
• Photothe ⁇ nogi-aphic materials were coated and dried as described in Example 1.
• the approximate phosphor coating weights were from 76 to 77 g/m 2 .
• the photothermographic materials were imaged, developed, and evaluated as described above in Example 1.
• the X-ray sensitometric response of these photothennographic materials was determined by exposing the samples using a Fischer X-ray unit operating at 200 n A and 76 KeV and filtered with a 3.0 mm sheet of aluminum. The samples were placed on a table set 85.5 cm fi-om the X-ray source. A series of X-ray exposures of constant intensity and exposure times from 0.1 sec to 1.5 sec were made. Exposed samples were developed in a manner similar to that described in Example 1. The density of these samples were measured with an X-Rite ® 310 densitometer using the Status A filters and measured with the visible filter.
• TABLE XXVI The sensitoinetric results, shown below in TABLE XXVI, demonstrate the increase in sensitivity to X-rays when the diphenylphosphine sulfide compounds are fonnulated along with gold(III) compounds in a phosphor-containing photothennographic material. The highest sensitivity to X-ray was obseived with addition of ZnBr 2 before the PS compound (PS-1). TABLE XXVI also shows the materials had good differentiation between developed density and Dmin. In addition, D log E curves showed low Dmin, and good speed and contrast.
• Example 15 Use in Photothermographic Materials Photothermographic emulsion and protective topcoat fonnulations were prepared as described in Example 13 above. The emulsion fonnulations were made with compound PS-1. The place in the preparation of the photothermographic fonnulation at which a solution of ZnBr 2 was added is shown in TABLE XXVII. The solution was added either as a solution of 0.169 g in 1.19 g of MeOH or as two additions of 0.0845 g in 0.595 g of MEOH. The photothe ⁇ nogi-aphic formulations were coated, dried, imaged, developed, and evaluated as described in Example 1.
• Example 16 Use in Phosphor-Containing Photothermographic Materials
• YSrTaO phosphor having an average size of 4.0 ⁇ m.
• the materials were mixed for 5 minutes to prepare the final photothennographic coating fonnulations.
• Photothennographic materials were coated and dried as described in Example 1.
• the approximate phosphor coating weights were fi-om 77 to 78 g/m".
• the photothennographic materials were imaged, developed, and evaluated as described above in Example 1.
• the X-ray sensitometric response of these photothe ⁇ nogi-aphic materials was dete ⁇ nined by exposing the samples using a Fischer X-ray unit operating at 200 mA and 76 KeV and filtered with a 3.0 mm sheet of aluminum.
• the samples were placed on a table set at 85.5 cm from the X-ray source.
• a series of X-ray exposures of constant intensity and exposure times from 0.1 sec to 1.5 sec were made.
• Exposed samples were developed in a manner similar to that described in Example 1.
• the density of these samples were measured with an X-rite 310 densitometer using the Status A filters and measured with the visible filter.
• TABLE XXIX The sensitometric results, shown below in TABLE XXIX, demonstrate the increase in sensitivity to X-rays when the diphenylphosphine sulfide compounds are fomiulated in a phosphor-containing photothemiographic material. The highest sensitivity to X-ray was observed with the placement of the ZnBr 2 split before and after PS-1 compound. TABLE XXIX also shows the materials had good differentiation between developed density and Dmin. hi addition, D log E curves showed low Dmin, and good speed and contrast.

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