EP0480568B1 - Nachverarbeitungsstabilisierung photothermographischer Emulsionen - Google Patents

Nachverarbeitungsstabilisierung photothermographischer Emulsionen Download PDF

Info

Publication number
EP0480568B1
EP0480568B1 EP19910307443 EP91307443A EP0480568B1 EP 0480568 B1 EP0480568 B1 EP 0480568B1 EP 19910307443 EP19910307443 EP 19910307443 EP 91307443 A EP91307443 A EP 91307443A EP 0480568 B1 EP0480568 B1 EP 0480568B1
Authority
EP
European Patent Office
Prior art keywords
silver
emulsion
post
pat
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19910307443
Other languages
English (en)
French (fr)
Other versions
EP0480568A2 (de
EP0480568A3 (en
Inventor
Larry R. C/O Minnesota Mining And Krepski
Kumars C/O Minnesota Mining And Sakizadeh
Sharon M. C/O Minnesota Mining And Simpson
David R c/o Minnesota Mining and Whitcomb
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0480568A2 publication Critical patent/EP0480568A2/de
Publication of EP0480568A3 publication Critical patent/EP0480568A3/en
Application granted granted Critical
Publication of EP0480568B1 publication Critical patent/EP0480568B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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

Definitions

  • This invention relates to photothermographic materials and in particular to post-processing stabilization of dry silver systems.
  • Silver halide photothermographic imaging materials especially "dry silver” compositions, processed with heat and without liquid development have been known in the art for many years.
  • Such materials are a mixture of light insensitive silver salt of an organic acid (e.g., silver behenate), a minor amount of catalytic light sensitive silver halide, and a reducing agent for the silver source.
  • the light sensitive silver halide is in catalytic proximity to the light insensitive silver salt such that the latent image formed by the irradiation of the silver halide serves as a catalyst nucleus for the oxidation-reduction reaction of the organic silver salt with the reducing agent when heated above 80°C.
  • Such media are described in U.S. Pat. Nos. 3,457,075; 3,839,049; and 4,260,677.
  • Toning agents can be incorporated to improve the color of the silver image of photothermographic emulsions as described in U.S. Pat. Nos. 3,846,136; 3,994,732 and 4,021,249.
  • Some of the problems with these stabilizers include thermal fogging during processing or losses in photographic sensitivity maximum density or contrast at stabilizer concentrations in which stabilization of the post-processed image can occur.
  • Stabilizer precursors have blocking or modifying groups that are usually cleaved during processing with heat and/or alkali. This provides the remaining moiety or primary active stabilizer to combine with the photoactive silver halide in the unexposed and undeveloped areas of the photographic material. For example, in the presence of a silver halide precursor in which the sulfur atom is blocked upon processing, the resulting silver mercaptide will be more stable than the silver halide to light, atmospheric and ambient conditions.
  • U.S. Patent No. 3,615,617 describes acyl blocked photographically useful stabilizers.
  • U.S. Patent Nos. 3,674,478 and 3,993,661 describe hydroxyarylmethyl blocking groups. Benzylthio releasing groups are described in U.S. Patent No. 3,698,898.
  • Thiocarbonate blocking groups are described in U.S. Patent No. 3,791,830, and thioether blocking groups in U.S. Patent Nos. 4,335,200, 4,416,977, and 4,420,554.
  • Photographically useful stabilizers which are blocked as urea or thiourea derivatives are described in U.S. Patent No. 4,310,612.
  • U.S. Patent Nos. 4,351,896 and 4,404,390 utilize carboxybenzylthio blocking groups for mesoionic 1,2,4-triazolium-3-thiolates stabilizers.
  • Photographic stabilizers which are blocked by a Michael-type addition to the carbon-carbon double bond of either acrylonitrile or alkyl acrylates are described in U.S. Patent Nos. 4,009,029 and 4,511,644, respectively. Heating of these blocked derivatives causes unblocking by a retro-Michael reaction.
  • novel azlactone-functional stabilizer precursor of Formula I and/or 2-alkenyl azlactones of Formula II and/or azlactones of Formula III into the photothermographic emulsion layer or a layer adjacent to the emulsion layer stabilizes the photoactive silver halide for improved post-processing stabilization without desensitizing or fogging the heat developable photographic material and process.
  • the general formulae I, II, and III describe such compounds thereof: wherein
  • Such compounds of Formula I are Michael reaction products of selected Michael donors (AH) to 2-alkenyl azlactone Michael acceptors (Formula II) as illustrated by a nitrogen nucleophile (IV) in the equation below, to an alkenyl azlactone Michael accepteor (V) to form a Michael adduct reaction product VI.
  • novel azlactone-functional stabilizer precursors of Formula I and/or the 2-alkenyl azlactones of Formula II and/or the azlactones of Formula III into the photothermographic emulsion layer or layer adjacent to the emulsion layer provides the photoactive silver halide emulsion with improved post-processing stability without desensitizing or fogging said emulsion.
  • A represents the residue of the "primary" post-processing stabilizer, AH, in which the hydrogen atom has been replaced by the azlactone functional "secondary" stabilizer.
  • the addition of the alkenyl azlactone to AH blocks the activity of the primary stabilizer AH, which left unblocked and added to the emulsion at the same molar equivalent would desensitize said emulsion.
  • the azlactone functional group releases the primary stabilizer providing improved post-processing stabilization from both the primary stabilizer and the secondary stabilizer, the azlactone moiety.
  • the primary stabilizer AH represents any group which links to the azlactone moiety by the loss of a hydrogen atom from a sulfur or nitrogen atom from the primary stabilizer.
  • AH has been defined as a post-processing stabilizing group.
  • This is a group, which when released from the azlactone, stabilizes the image formed after processing.
  • the group could not have been originally associated with the emulsion as the compound A-H because that compound would have been too active and would have actively suppressed image formation.
  • the combination of processing heat in the presence of the photothermographic environment releases the group A from the azlactone at a useful time.
  • the presence of azlactone group itself can give some post-processing stability.
  • Post-processing stabilizing groups usually have a sulfur or nitrogen atom available for complexing silver ion.
  • the compounds are usually ring structures with the sulfur and/or nitrogen within the ring or external to the ring. These compounds are well known to the ordinary skilled photographic chemist.
  • Suitable stabilizers are well known in the art such as nitrogen-containing substituted or unsubstituted heterocyclic rings; such as benzimidazole, benzotriazole; triazoles; tetrazoles; imidazoles; various mercapto-containing substituted or unsubstituted compounds; such as mercapto triazoles, mercapto tetrazoles; thio-substituted heterocycles; or any such compound that stabilizes the said emulsion but at such concentrations desensitizes the initial sensitometric response if left unblocked. Many of such compounds are summarized in Research Disclosure 29963 from March, 1989 entitled "Photothermographic Silver Halide Systems".
  • novel azlactone-functional stabilizer precursors of Formula I and 2-alkenyl azlactones or Formula II are shown by the formulae below, which, however, does not limit the compounds to be used in the present invention.
  • Examples of suitable 2-alkenyl azlactones of Formula II include: 2-vinyl-4,4-dimethyl-2-oxazolin-5-one (II-A (VDM)), 2-isopropenyl-4,4-dimethyl-2-oxazolin-5-one, 2-vinyl-4-ethyl-4-methyl-2-oxazolin-5-one, 2-vinyl-4,4-dimethyl-1,3-oxazin-6-one and others disclosed in U.S. Patent No. 4,304,705.
  • the preferred 2-alkenyl azlactones is VDM (available from SNPE, Inc., Princeton, NJ).
  • Suitable azlactones of Formula III include: 2-methyl-4,4-dimethyl-2-oxazolin-5-one, 2-ethyl-4,4-dimethyl-2-oxazolin-5-one, 2-isopropyl-4-ethyl-4-methyl-2-oxazolin-5-one, 2-phenyl-4,4-dimethyl-2-oxazolin-5-one, 2-ethyl-4,4-dimethyl-1,3-oxazin-6-one, and others described by Y. S. Rao and R. Filler in a review entitled "Oxazolones" contained in "Heterocyclic Compounds, Vol. 45" edited by I. J.
  • VDM (2-vinyl-4,4-dimethylazlactone) (13.9 g, 0.10 mole) and 1-phenyl-1H-tetrazole-5-thiol (17.8 g, 0.1 mole) was heated at 100°C overnight to yield the desired product.
  • VDM (13.9 g, 0.10 mole) was cooled to 0°C and mixed with 1-phenyl-1H-tetrazole-5-thiol (17.8 g, 0.10 mole). The mixture was allowed to warm to room temperature and kept at this temperature overnight to give a quantitive yield of the desired product as a white solid. Structure of the product was confirmed by spectral analyses.
  • the amounts of the above described compounds according to the present invention which are added can be varied depending upon the particular compound used and upon the photothermographic emulsion-type. However, they are preferably added in an amount of 10 -3 to 50 mol, and more preferably from 10 -2 to 10 mol, per mol of silver halide in the emulsion layer.
  • the photothermographic dry silver emulsions of this invention may be constructed of one or more layers on a substrate.
  • Single layer constructions must contain the silver source material, the silver halide, the developer and binder as well as optional additional materials such as toners, coating aids and other adjuvants.
  • Two-layer constructions must contain the silver source and silver halide in one emulsion layer (usually the layer adjacent the substrate) and some of the other ingredients in the second layer or both layers.
  • Multicolor photothermographic dry silver constructions contain sets of these bilayers for each color. Color forming layers are maintained distinct from each other by the use of functional or non-functional barrier layers between the various photosensitive layers as described in U.S. Pat. No. 4,460,681.
  • the silver source material may be any material which contains a reducible source of silver ions.
  • Silver salts of organic acids particularly long chain (10 to 30, preferably 15 to 28 carbon atoms) fatty carboxylic acids are preferred.
  • Complexes of organic or inorganic silver salts wherein the ligand has a gross stability constant between 4.0 and 10.0 are also desirable.
  • the silver source material constitutes from about 5 to 30 percent by weight of the imaging layer.
  • the second layer in a two-layer construction or in the bilayer of a multi-color construction would not affect the percentage of the silver source material desired in the photosensitive single imaging layer.
  • the organic silver salt which can be used in the present invention is a silver salt which is comparatively stable to light, but forms a silver image when heated to 80°C or higher in the presence of an exposed photocatalyst (such as silver halide) and a reducing agent.
  • Suitable organic silver salts include silver salts of organic compounds having a carboxy group. Preferred examples thereof include a silver salt of an aliphatic carboxylic acid and a silver salt of an aromatic carboxylic acid. Preferred examples of the silver salts of aliphatic carboxylic acids include silver behenate, silver stearate, silver oleate, silver laurate, silver caprate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartarate, silver furoate, silver linoleate, silver butyrate and silver camphorate, mixtures thereof, etc. Silver salts which are substituted with a halogen atom of a hydroxyl group can also be effectively used.
  • Preferred examples of the silver salts of aromatic carboxylic acid and other carboxyl group-containing compounds include silver benzoate, a silver substituted benzoate such as silver 3,5-dihydroxybenzoate, silver o-methylbenzoate, silver m-methylbenzoate, silver p-methylbenzoate, silver 2,4-dichlorobenzoate, silver acetamidobenzoate, silver p-phenyl benzoate, etc., silver gallate, silver tannate, silver phthalate, silver terephthalate, silver salicylate, silver phenylacetate, silver pyromellitate, a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione or the like as described in U.S. Pat. No. 3,785,830, and silver salt of an aliphatic carboxylic acid containing a thioether group as described in U.S. Pat. No. 3,330,663, etc.
  • Silver salts of compounds containing mercapto or thione groups and derivatives thereof can be used.
  • Preferred examples of these compounds include a silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, a silver salt of 2-mercaptobenzimidazole, a silver salt of 2-mercapto-5-aminothiadiazole, a silver salt of 2-(S-ethylglycolamido) benzothiazole, a silver salt of thioglycolic acid such as a silver salt of a S-alkyl thioglycolic acid (wherein the alkyl group has from 12 to 22 carbon atoms) as described in Japanese patent application No.
  • a silver salt of a dithiocarboxylic acid such as a silver salt of dithioacetic acid, a silver salt of thioamide, a silver salt of 5-carboxylic-1-methyl-2-phenyl-4-thiopyridine, a silver salt of mercaptotriazine, a silver salt of 2-mercaptobenzoxazole, a silver salt as described in U.S. Pat. No.
  • a silver salt of 1,2,4-mercaptothiazole derivative such as a silver salt of 3-amino-5-benzylthio-1,2,4-thiazole
  • a silver salt of thione compound such as a silver salt of 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-thione as disclosed in U.S. Pat. No. 3,301,678.
  • a silver salt of a compound containing an imino group can be used.
  • Preferred examples of these compounds include a silver salt of benzothiazole and a derivative thereof as described in Japanese patent publications Nos. 30270/69 and 18146/70, for example, a silver salt of benzothiazole such as silver salt of methylbenzotriazole, etc., a silver salt of a halogen substituted benzotriazole, such as a silver salt of 5-chlorobenzotriazole, etc., a silver salt of carboimidobenzotriazole, etc., a silver salt of 1,2,4-triazole, of 1-H-tetrazole as described in U.S. Pat. No. 4,220,709, a silver salt of imidazole and an imidazole derivative, and the like.
  • silver halfsoaps of which an equimolar blend of silver behenate and behenic acid, prepared by precipitation from aqueous solution of the sodium salt of commercial behenic acid and analyzing about 14.5 percent silver, represents a preferred example.
  • Transparent sheet materials made on transparent film backing require a transparent coating and for this purpose the silver behenate full soap, containing not more than about four or 5 percent of free behenic acid and analyzing about 25.2 percent silver may be used.
  • the light sensitive silver halide used in the present invention can be employed in a range of 0.0005 mol to 5 mol and, preferably, from 0.005 mol to 1.0 mol per mol of organic silver salt.
  • the silver halide may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide, etc.
  • the silver halide used in the present invention may be employed without modification. However, it may be chemically sensitized with a chemical sensitizing agent such as a compound containing sulphur, selenium or tellurium etc., or a compound containing gold, platinum, palladium, rhodium or iridium, etc., a reducing agent such as a tin halide, etc., or a combination thereof.
  • a chemical sensitizing agent such as a compound containing sulphur, selenium or tellurium etc., or a compound containing gold, platinum, palladium, rhodium or iridium, etc.
  • a reducing agent such as a tin halide, etc.
  • the silver halide may be added to the emulsion layer in any fashion which places it in catalytic proximity to the silver source.
  • the silver halide and the organic silver salt which are separately formed in a binder can be mixed prior to use to prepare a coating solution, but it is also effective to blend both of them in a ball mill for a long period of time. Further, it is effective to use a process which comprises adding a halogen-containing compound in the organic silver salt prepared to partially convert the silver of the organic silver salt to silver halide.
  • preformed silver halide emulsions of this invention can be unwashed or washed to remove soluble salts.
  • the soluble salts can be removed by chill-setting and leaching or the emulsion can be coagulation washed, e.g., by the procedures described in Hewitson, et al., U.S. Pat. No. 2,618,556; Yutzy et al., U.S. Pat. No. 2,614,928; Yackel, U.S. Pat. No. 2,565,418;; Hart et al., U.S. Pat. No. 3,241,969; and Waller et al., U.S. Pat. No. 2,489,341.
  • the silver halide grains may have any crystalline habit including, but not limited to cubic, tetrahedral, orthorhombic, tabular, laminar, platelet, etc.
  • Photothermographic emulsions containing preformed silver halide in accordance with this invention can be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds, or combinations of these.
  • chemical sensitizers such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds, or combinations of these.
  • Suitable chemical sensitization procedures are described in Shepard, U.S. Pat. No. 1,623,499; Waller, U.S. Pat. No. 2,399,083; McVeigh, U.S. Pat. No. 3,297,447; and Dunn, U.S. Pat. No. 3,297,446.
  • the light-sensitive silver halides can be spectrally sensitized with various known dyes including cyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes.
  • Useful cyanine dyes include those having a basic nucleus, such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus.
  • Useful merocyanine dyes which are preferred include those having not only the above described basic nuclei but also acid nuclei, such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a nalonitrile nucleus and a pyrazolone nucleus.
  • acid nuclei such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a nalonitrile nucleus and a pyrazolone nucleus.
  • the sensitizing dye to be used in the present invention is properly selected from known dyes as described in U.S. Pat. No. 3,761,279, 3,719,495 and 3,877,943, British Pat Nos. 1,466,201, 1,469,117 and 1,422,057, Japanese Patent Application (OPI) Nos. 27924/76 and 156424/75, and so on, and can be located in the vicinity of the photocatalyst according to known methods used in the above-described examples.
  • These spectral sensitizing dyes are used in amounts of about 10 -4 mol to about 1 mol per 1 mol of photocatalyst.
  • the reducing agent for silver ion may be any material, preferably organic material, which will reduce silver ion to metallic silver.
  • Conventional photographic developers such as phenidone, hydroquinones, and catechol are useful but hindered phenol reducing agents are preferred.
  • the reducing agent should be present as 1 to 10 percent by weight of the imaging layer. In a two-layer construction, if the reducing agent is in the second layer, slightly high proportions, of from about 2 to 15 percent tend to be more desirable.
  • amidoximes such as phenylamidoxime, 2-thienylamidoxime and p-phenoxyphenylamidoxime, azine, e.g., 4-hydroxy-3,5-dimethoxybenzaldehyde azine; a combination of aliphatic carboxylic acid aryl hydrazides and ascorbic acid, such as 2,2-bis(hydroxymethyl)propionyl-beta-phenyl hydrazide in combination with ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, a reductone and/or a hydrazine, e.g., a combination of hydroquinone and bis(ethoxyethyl)hydroxylamine, piperidinohexose reductone or formyl-4-methylphenyl hydrazine, hydroxamic acids such as phenylhydroxamic acid, p-hydroxyphenyl hydroxa
  • Toner materials may be present, for example, in amounts from 0.1 to 10 percent by weight of all silver bearing components. Toners are well known materials in the photothermographic art as shown in U.S. Pat. Nos. 3,080,254; 3,847,612 and 4,123,282.
  • toners include phthalimide and N-hydroxyphthalimide; cyclic imides such as succinimide, pyrazoline-5-ones, and a quinazolinone, 3-phenyl-2-pyrazoline-5-one, 1-phenylurazole, quinazoline, and 2,4-thiazolidinedione; naphthalimides, e.g., N-hydroxy-1,8-naphthalimide; cobalt complexes, e.g., cobaltic hexamine trifluoroacetate; mercaptans as illustrated by 3-mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N-(aminomethyl)aryl dicarboximides, e.g.
  • N-dimethylaminomethyl)phthalimide and N-(dimethylaminomethyl)naphthalene-2,3-dicarboximide; and a combination of blocked pyrazoles, isothiuronium derivatives and certain photobleach agents, e.g., a combination of N,N'-hexamethylene bis(1-carbamoyl-3,5-dimethylpyrazole), 1,8-(3,6-diazaoctane)bis(isothiuronium trifluoroacetate) and 2-(tribromomethylsulphonyl)-benzothiazole); and merocyanine dyes such as 3-ethyl-5[(3-ethyl-2-benzothiazolinylidene)-1-methylethylidene]-2-thio-2,4-oxazolidinedione; phthalazinone, phthalazinone derivatives or metal salts or these derivatives such as 4-(1-naph
  • Coupler materials e.g., a combination of silver benzotriazole, well known magenta, yellow and cyan dye-forming couplers, aminophenol developing agents, a base release agent such as guanidinium trichloroacetate and silver bromide in poly(vinyl butyral); a combination of silver bromoiodide, sulphonamidophenol reducing agent, silver behenate, poly(vinyl butyral), an amine such as n-octadecylamine and 2-equivalent or 4-equivalent cyan, magenta or yellow dye-forming couplers; incorporating leuco dye bases which oxidize to form a dye image, e.g., Malachite Green, Crystal Violet and pararosaniline; a combination of in situ silver halide, silver behenate, 3-methyl-1-phenylpyrazolone and N,N'-dimethyl-p-
  • Silver halide emulsions containing the stabilizers of this invention can be protected further against the additional production of fog and can be stabilized against loss of sensitivity during keeping.
  • Suitable anti-foggants and stabilizers which can be used alone or in combination, include the thiazolium salts described in Staud, U.S. Pat. No. 2,131,038 and Allen U.S. Pat. No. 2,694,716; the azaindenes described in Piper, U.S. Pat. No. 2,886,437 and Heimbach, U.S. Pat. No. 2,444,605; the mercury salts described in Allen, U.S. Pat. No. 2,728,663; the urazoles described in Anderson, U.S. Pat. No.
  • Stabilized emulsions of the invention can contain plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton, U.S. Pat. No. 2,960,404; fatty acids or esters such as those described in Robins, U.S. Pat. No. 2,588,765 and Duane, U.S. Pat. No. 3,121,060; and silicone resins such as those described in DuPont British Patent No. 955,061.
  • plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton, U.S. Pat. No. 2,960,404; fatty acids or esters such as those described in Robins, U.S. Pat. No. 2,588,765 and Duane, U.S. Pat. No. 3,121,060; and silicone resins such as those described in DuPont British Patent No. 955,061.
  • the photothermographic elements can include image dye stabilizers.
  • image dye stabilizers are illustrated by U.K. Patent No. 1,326,889; Lestina et al. U.S. Pat. Nos. 3,432,300 and 3,698,909; Stern et al. U.S. Pat. No. 3,574,627; Brannock et al. U.S. Pat. No. 3,573,050; Arai et al. U.S. Pat. No. 3,764,337 and Smith et al. U.S. Pat. No. 4,042,394.
  • Photothermographic elements containing emulsion layers stabilized according to the present invention can be used in photographic elements which contain light absorbing materials and filter dyes such as those described in Sawdey, U.S. Pat. No. 3,253,921; Gaspar U.S. Pat. No. 2,274,782; Carroll et al., U.S. Pat. No. 2,527,583 and Van Campen, U.S. Pat. No. 2,956,879.
  • the dyes can be mordanted, for example, as described in Milton and Jones, U.S. Pat. No. 3,282,699.
  • Photothermographic elements containing emulsion layers stabilized as described herein can contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et al., U.S. Pat. No. 2,992,101 and Lynn, U.S. Pat. No. 2,701,245.
  • matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et al., U.S. Pat. No. 2,992,101 and Lynn, U.S. Pat. No. 2,701,245.
  • Emulsions stabilized in accordance with this invention can be used in photothermographic elements which contain antistatic or conducting layers, such as layers that comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk, U.S. Pat. Nos. 2,861,056, and 3,206,312 or insoluble inorganic salts such as those described in Trevoy, U.S. Pat. No. 3,428,451.
  • antistatic or conducting layers such as layers that comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk, U.S. Pat. Nos. 2,861,056, and 3,206,312 or insoluble inorganic salts such as those described in Trevoy, U.S. Pat. No. 3,428,451.
  • the binder may be selected from any of the well-known natural or synthetic resins such as gelatin, polyvinyl acetals, polyvinyl chloride, polyvinyl acetate, cellulose acetate, polyolefins, polyesters, polystyrene, polyacrylonitrile, polycarbonates, and the like. Copolymers and terpolymers are of course included in these definitions.
  • the preferred photothermographic silver containing polymer is polyvinyl butyral, butethyl cellulose, methacrylate copolymers, maleic anhydride ester copolymers, polystyrene, and butadiene-styrene copolymers.
  • these polymers may be used in combination of two or more thereof.
  • Such a polymer is used in an amount sufficient to carry the components dispersed therein, that is, within the effective range of the action as the binder.
  • the effective range can be appropriately determined by one skilled in the art.
  • a preferable ratio of the binder to the organic silver salt ranges from 15:1 to 1:2, and particularly from 8:1 to 1:1.
  • Photothermographic emulsions containing the stabilizer of the invention can be coated on a wide variety of supports.
  • Typical supports include polyester film, subbed polyester film, poly(ethylene terephthalate)film, cellulose nitrate film, cellulose ester film, poly(vinyl acetal) film, polycarbonate film and related or resinous materials, as well as glass, paper metal and the like.
  • a flexible support is employed, especially a paper support, which can be partially acetylated or coated with baryta and/or an alphaolefin polymer, particularly a polymer of an alpha-olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.
  • the substrate with backside resistive heating layer may also be used in color photothermographic imaging systems such as shown in U.S. Pat. No. 4,460,681 and 4,374,921.
  • Photothermographic emulsions of this invention can be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type descirbed in Benguin, U.S. Pat. No. 2,681,294. If desired, two or more layers may be coated simultaneously by the procedures described in Russell, U.S. Pat. No. 2,761,791 and Wynn British Patent No. 837,095.
  • a dispersion of silver behenate half soap was made at 10% solids in toluene and acetone by homogenization.
  • To 127g of this silver half soap dispersion was added 252g methyl ethyl ketone, 104g isopropyl alcohol and 0.5g of polyvinylbutyral.
  • 4 ml of mercuric bromide (.36/10 ml methanol) were added.
  • 8.0 ml of calcium bromide (.236g/10ml methanol) was added 30 minutes later.
  • 27.0 g of polyvinylpyrrolidone was added, and 27.0 g of polyvinylbutyral was added one hour later.
  • the samples were exposed for 10 -3 seconds through a 47B Wratten filter and a 0 to 3 continuous wedge and developed by heating to approximately 138°C for 6 seconds.
  • the density of the dye was measured using a blue filter of a computer densitometer.
  • Post-processing stability was measured by exposing imaged samples to 1200 ft-candles of illumination for 6 hours at 65% relative humidity and 26.7°C.
  • the initial sensitometric data are shown below: Dmin Dmax Speed Contrast Control (0.0ml) 0.13 2.47 1.99 5.54 0.2 ml I-A 0.14 2.34 1.94 6.13 1.0 ml I-A 0.14 1.68 1.96 4.41 0.2 ml I-B 0.13 2.39 1.93 6.26 1.0 ml I-B 0.13 1.73 2.01 4.43
  • the post-processing print stability results are shown below: ⁇ Dmin ⁇ Dmax Control (0.0ml) +0.53 -0.10 0.2 ml I-A +0.33 -0.13 1.0 ml ml I-A +0.26 -0.11 0.2 ml I-B +0.36 -0.10 1.0 ml I-B +0.25 -0.10
  • a greater than 32% Dmin post-processing improvement vs. unstabilized control was observed without any effect on initial sensitometric responses.
  • Example 2 To 9.9 g of the yellow silver halide coating solution as described in Example 1 was added 0.5 ml or 1.0 ml of 1-phenyl-5-mercapto-tetrazole (PMT) at a concentration of 0.1 g/5 ml methanol. The silver solutions and topcoats were coated, exposed and procesed as described in Example 1. The initial sensitometric data are shown below. Dmin Dmax Speed Contrast Control (0.0 ml) 0.13 2.30 2.03 4.94 0.5 ml PMT 0.13 1.72 2.15 4.06 Control (0.0 ml) 0.13 2.47 1.99 5.54 1.0 ml PMT 0.13 0.81 2.64 --
  • PMT 1-phenyl-5-mercapto-tetrazole
  • Example 1 At these concentrations of PMT, significant desensitization of the silver halide emulsion has occured for post-processing Dmin improvement greater than 40%.
  • PMT was significantly blocked by the azlactone group to minimize any desensitization effects but still allowed the release of PMT for the Dmin post-processing improvements observed in Example 1-A with the unblocked PMT stabilizer.
  • Example 2 To 9.9 g of the yellow silver halide coating solution as described in Example 1 was added 1.0 of compound II-A at a concentration of 0.1 g/5 ml in methanol. The silver solutions and topcoats were coated, exposed, and processed as described in Example 1. The initial sensitometric data are shown below. Dmin Dmax Speed Contrast Control (0.0 ml) 0.12 2.22 1.84 4.52 1.0 ml II-A 0.11 2.26 1.79 4.94
  • the post processing print stability was measured as described in Example 1 and the results are shown below.
  • compound II-A improves the Dmin post-processing stability approximately 10%.
  • the compound II-A functions as a post-processing stabilizer and will contribute to the overall post-processing Dmin improvement as the blocking moiety to post-processing stabilizer precursors.
  • Example 2 To 9.9 g of a yellow silver halide solution similar to Example 1, was added 0.2 ml or 0.5 ml of compound I-E at a concentration of 0.2 g/5 ml of methanol. A similar topcoat was coated over the yellow silver layer as described in Example 1. The coatings were exposed and processed as described in Example 1 and the initial sensitometric data are shown below.
  • Dmin Dmax Speed Contrast Control (0.0 ml) 0.11 2.46 1.77 5.09 0.2 ml I-E 0.13 2.41 1.77 4.77 0.5 ml I-E 0.15 2.25 1.79 3.50
  • the post-processing results are shown below.
  • a magenta color-forming silver halide dispersion was prepared by using 502 g of the silver half soap dispersion of Example 1 and adding 0.4 g of polyvinylbutyral. After 15 minutes of mixing, a 0.5 g/9.75 g mercuric acetate in methanol solution and a 0.55g/18.4 g calcium bromide in methanol solution wee added. Then an additional 0.55 g/18.4 g calcium bromide in methanol solution was added 30 minutes later. After 45 minutes of mixing, 49.8 g of polyvinylbutyral was added.
  • magenta silver coating solution To 10.0 g of the magenta silver coating solution was added 0.2 ml or 1.0 ml of compound I-C at a concentration of 0.2 g/5 ml of methanol.
  • the magenta silver layer and topcoat are coated simultaneously at a wet thickness of 2 mils, respectively and dried for 5 minutes at 82°C.
  • the samples were exposed for 10 -3 seconds through a 58 Wratten filter and a 0 to 3 continuous wedge and developed by heating to approximately 138°C for 6 seconds.
  • the density of the dye for each sample was measured using a green filter of a computer densitometer.
  • Post-processing stability was measured by exposing imaged samples to 1200 ft-candles of illumination for 7 hours at 65% relative humidity and 26.7°C. The initial sensitometric data are shown below.
  • Dmin Dmax Speed Contrast Control (0.0 ml) 0.11 1.76 2.03 2.12 0.2 ml I-C 0.11 1.74 2.04 2.16 1.0 ml I-C 0.12 1.12 2.83 1.38
  • the post-processing print stability was measured and the results are shown below.
  • Example 4 To 10.0 g of the magenta silver halide coating solution as described in Example 4, was added 0.35 ml or 1.0 ml of benzimidazole (BI) at a concentration of 0.1 g/5 ml of methanol. The silver solutions and topcoat were coated, exposed, and processed as described in Example 4. The initial sensitometric data are shown below.
  • Dmin Dmax Speed Contrast Control (0.0 ml) 0.09 1.71 1.96 1.87 0.35 ml BI 0.09 1.60 2.29 1.77 1.0 ml BI 0.08 1.25 2.72 1.44
  • the post-processing print stability was measured as described in Example 4 and the results are shown below.
  • ⁇ Dmin ⁇ Dmax Control (0.0 ml) +0.16 -0.22 0.35 ml BI +0.14 -0.27 1.0 ml BI +0.10 -0.31
  • Example 4 BI was significantly blocked (0.2 ml) by the azlactone group to minimize any desensitization effects but still allowed the release of BI for the Dmin post-processing improvements observed in Example 4-A with the unblocked BI stabilizer.
  • a two color formulation was studied with compound I-D.
  • a similar topcoat was coated over the yellow silver layer as described in Example 1.
  • a magenta color-forming silver halide layer and topcoat as described in Example 4 were coated simultaneously over the yellow topcoat. The samples were exposed and processed as described in Example 1. The initial sensitometric data are shown below.
  • Example 5 To 10.0 g of the yellow silver halide coating solution described in Example 5, ws added 1.0 ml of 3-trifluoromethyl-4-methyl-5-mercapto-1,2,4-triazole (MFT) at a concentration of 0.2 g/4 ml of ethanol. The topcoat, magenta silver and topcoat solutions were coated over the yellow silver halide layer as described in Example 5. The samples were exposed and processed as described in Example 1. The initial sensitometric data are shown below. Dmin Dmax Speed Contrast Control (0.0 ml) 0.13 1.73 1.95 3.63 1.0 ml MFT 0.15 .63 -- -- The post-processing print stability was measured and the results are shown below. ⁇ Dmin ⁇ Dmax Control (0.0 ml) +0.51 -0.02 1.0 ml MFT +0.24 --
  • MFT 3-trifluoromethyl-4-methyl-5-mercapto-1,2,4-triazole
  • Example 5 MFT was blocked by the azlactone group to minimize any desensitization effects but still allowed the release of MFT for the Dmin post-processing improvements observed in Example 5-A with the unblocked MFT stabilizer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Claims (10)

  1. Photothermographische Emulsion, umfassend ein photographisches Silberhalogenid, Silber-Ausgangsmaterial, Reduziermittel für Silberion, Bindemittel und eine die Nachbearbeitung stabilisierende Menge eines Azlactons von 0,001 ... 50 Mol pro Mol Silberhalogenid in der Emulsion, dargestellt durch eine der Formeln:
    Figure 00380001
    Figure 00380002
    worin sind:
    A ein Rest der die Nachbearbeitung stabilisierenden Gruppe, in der ein Wasserstoffatom des Nachbearbeitungsstabilisators durch den Rest der in Formel I gezeigten Struktur ersetzt wurde;
    R1, R2 und R3 unabhängig Wasserstoff oder Methyl und mit der Voraussetzung, daß R1 eine Aryl-Gruppe darstellen kann, wenn R2 und R3 Wasserstoff sind;
    R4 und R5 unabhängig eine Alkyl-Gruppe, eine Cycloalkyl-Gruppe, eine Aryl-Gruppe oder R4 und R5 bilden gemeinsam mit dem Kohlenstoff-Atom, an dem verbunden sind, einen Ring von 4 bis 12 Kohlenstoff-Atomen;
    R6 und R7 unabhängig Wasserstoff oder niederes Alkyl, vorzugsweise C1...C4-Alkyl;
    R8 eine beliebige organische Gruppe, wie beispielsweise Alkyl-Gruppen (z.B. mit 1 ... 20 Kohlenstoff-Atomen, mehr bevorzugt mit 1 ... 12 Kohlenstoff-Atomen und einschließend Cycloalkyl mit 2 ... 20 Kohlenstoff-Atomen, vorzugsweise mit 5 ... 8 Kohlenstoff-Atomen), Aryl-Gruppen (z.B. mit bis zu 7 Ringatomen) und heterocyclische Gruppen (vorzugsweise C-, S-, N-, O- und Se-Atome mit bis zu 7 Ringatomen); sowie
    n Null oder 1.
  2. Emulsion nach Anspruch 1, worin das Azlacton durch Formel I dargestellt wird.
  3. Emulsion nach Anspruch 1, worin das Azlacton durch Formel II dargestellt wird.
  4. Emulsion nach Anspruch 1, worin das Azlacton durch Formel III dargestellt wird.
  5. Emulsion nach Anspruch 1, worin das Silber-Ausgangsmaterial das Silbersalz einer organischen Säure umfaßt.
  6. Emulsion nach Anspruch 2, 3 oder 4, worin das Silber-Ausgangsmaterial Silberbehenat umfaßt.
  7. Emulsion nach Anspruch 2, 3 oder 4, worin n gleich eins ist.
  8. Emulsion nach Anspruch 2, 3 oder 4, worin n gleich Null ist.
  9. Emulsion nach Anspruch 2, 3 oder 4, worin A ausgewählt aus der Gruppe, bestehend aus Benzotriazolen, Benzimidazolen, Triazolen, Tetrazolen, Imidazolen, Mercaptotetrazolen, Mercaptotriazolen und Thio-substituierten Heterocyclen.
  10. Emulsion nach Anspruch 6, worin A ausgewählt aus der Gruppe, bestehend aus Benzotriazolen, Benzimidazolen, Triazolen, Tetrazolen, Imidazolen, Mercaptotetrazolen, Mercaptotriazolen und Thio-substituierten Heterocyclen.
EP19910307443 1990-08-31 1991-08-13 Nachverarbeitungsstabilisierung photothermographischer Emulsionen Expired - Lifetime EP0480568B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US57583490A 1990-08-31 1990-08-31
US575834 1990-08-31

Publications (3)

Publication Number Publication Date
EP0480568A2 EP0480568A2 (de) 1992-04-15
EP0480568A3 EP0480568A3 (en) 1995-12-06
EP0480568B1 true EP0480568B1 (de) 1998-06-10

Family

ID=24301896

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910307443 Expired - Lifetime EP0480568B1 (de) 1990-08-31 1991-08-13 Nachverarbeitungsstabilisierung photothermographischer Emulsionen

Country Status (5)

Country Link
EP (1) EP0480568B1 (de)
JP (1) JP3051865B2 (de)
AU (1) AU642284B2 (de)
CA (1) CA2049203A1 (de)
DE (1) DE69129573T2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107899077A (zh) * 2017-12-20 2018-04-13 四川大学 一种稳定性增强的复合抗菌涂层及其制备方法和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5158866A (en) * 1990-08-31 1992-10-27 Minnesota Mining And Manufacturing Company Post-processing stabilization of photothermographic emulsions with amido compounds
US5300420A (en) * 1993-06-01 1994-04-05 Minnesota Mining And Manufacturing Company Stabilizers for photothermography with nitrile blocking groups
US5298390A (en) * 1993-06-07 1994-03-29 Minnesota Mining And Manufacturing Company Speed enhancers and stabilizers for photothermography

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3169465D1 (en) * 1980-12-12 1985-04-25 Eastman Kodak Co Photographic material containing a silver halide stabilizer precursor compound
US4378442A (en) * 1982-03-17 1983-03-29 Marsh Andrew J Polysulphide sealants
US4459350A (en) * 1982-09-29 1984-07-10 Eastman Kodak Company Photothermographic material and processing comprising a substituted triazine
US5149806A (en) * 1990-03-28 1992-09-22 Minnesota Mining And Manufacturing Company Azlactone michael adducts

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107899077A (zh) * 2017-12-20 2018-04-13 四川大学 一种稳定性增强的复合抗菌涂层及其制备方法和应用
CN107899077B (zh) * 2017-12-20 2019-08-09 四川大学 一种稳定性增强的复合抗菌涂层及其制备方法和应用

Also Published As

Publication number Publication date
EP0480568A2 (de) 1992-04-15
CA2049203A1 (en) 1992-03-01
DE69129573T2 (de) 1998-12-24
JPH04234750A (ja) 1992-08-24
AU642284B2 (en) 1993-10-14
DE69129573D1 (de) 1998-07-16
AU8178691A (en) 1992-03-05
EP0480568A3 (en) 1995-12-06
JP3051865B2 (ja) 2000-06-12

Similar Documents

Publication Publication Date Title
US5175081A (en) Post-processsing stabilization of photothermographic emulsions
EP0473351B1 (de) Nachverarbeitungs Stabilisierung photographische Emulsionen mit Amidoverbindungen
US5464737A (en) Post-processing stabilizers for photothermographic articles
EP0542850B1 (de) Nach der verarbeitung stabilisiertes photothermographisches aufzeichnungs-material
JP3249664B2 (ja) 光熱写真エレメント
EP0533008B1 (de) Chromogene Blaugrünleukofarbstoffe für photothermographische Materialien
US5298390A (en) Speed enhancers and stabilizers for photothermography
US5300420A (en) Stabilizers for photothermography with nitrile blocking groups
EP0533007B1 (de) Wärmeentwickelbare photographische Elemente
EP0480568B1 (de) Nachverarbeitungsstabilisierung photothermographischer Emulsionen
EP0542763B1 (de) Nachverarbeitungsstabilisierung photothermographischer emulsionen
JPH0777771A (ja) シリルブロック基を含む熱写真成分
US5681693A (en) Post processing stabilization of photothermographic emulsions
EP0588717A2 (de) Stabilisatoren für die Nachbehandlung von photothermographischen Artikeln

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB IT NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB IT NL

17P Request for examination filed

Effective date: 19960607

17Q First examination report despatched

Effective date: 19960729

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 19980610

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980610

REF Corresponds to:

Ref document number: 69129573

Country of ref document: DE

Date of ref document: 19980716

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19990802

Year of fee payment: 9

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20000703

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010430

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010813

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20010813

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20050831

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070301