Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/485—Direct positive emulsions
  • G03C1/48515—Direct positive emulsions prefogged
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F28/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
• • 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
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

• This invention relates to photographic materials, their preparation and use. In one of its aspects, this invention relates to improved photographic silver halide solarizing emulsion layers and photographic elements containing these layers. In a specific aspect, this invention relates to fogged, direct-positive photographi silver halide emulsion layers having a binding agent comprising a hydrophilic colloid and a water-insoluble polymerized vinyl compound.
• Still another object of this invention is to provide a photographic element bearing a layer of a fogged, direct-positive photographic silver halide emulsion having a binding agent comprising a hydrophilic colloid and a water-inso uble polymerized vinyl compound.
• One embodiment of this invention relates to a fogged, direct-positive photographic silver halide emulsion in which the binding agent comprises a hydrophilic colloid "ice and an aqueous dispersion of polymerized vinyl com pound.
• Another embodiment of this invention relates to a photographic element comprising a support and at least one fogged, direct-positive photographic silver halide emulsion layer in which the binding agent comprises a hydrophilic colloid and water-insoluble polymerized vinyl compound.
• One component of the binding agent for the photographic silver halide emulsions described herein is an aqueous dispersion of polymeric vinyl compound.
• the preferred polymeric vinyl compounds are homo or copolymers prepared from acrylic acid and esters thereof. These polymers are insoluble in water and can be readily dispersed in water and mixed with a suitable hydrophilic colloid such as gelatin.
• the vinyl polymers are generally employed in concentrations in the range of about 20 to about most often concentrations at least 50%, by weight, based on the combined weight of hydrophilic colloid and polymerized vinyl compound.
• the remainder of the binding agent is a hydrophilic colloid such as gelatin, alone or with another photographic binding mat rial.
• a polymeric vinyl compound which contains, in polymerized form, at least 65%, preferably about 75 to about by weight, of an alkyl acrylate or methacrylate, as exemplified by ethyl acrylate, methyl acrylate, butyl acrylate, ethyl methacrylate, octyl 'methacrylate, and the like.
• Suitable ethylenically unsaturated comonomers which can be interpolymer ized with these materials to form water-insoluble addi 1 tion polymers include, for exampl vinyl esters, amides.
• nitriles ketones, halides, ethers, e o-unsaturated acids or esters thereof, olefins, diolefins and the like, as exemplified by acrylonitrile, methacrylonitrile, styrene, tat-methylstyrene, vinyl chloride, vinylidene chloride, methyl vinyl ketone, vinyl acetate, fumaric, maleic and itaconic acid esters, 2 chloroethylvinylether, methylenemaleonitrile, acrylic acid, methacrylic acid, dimethylaminoethylmethacrylate, N-vinylsuccinimide, N-vinylphthalimide, N- vinylpyrrolidone, butadiene, isoprene, vinylidene cyanide and the like.
• the polymeric vinyl compounds most useful in the practice of this invention generally have an average molecular weight in the range of about 5000 to about 500,000 and a particle size in the dispersion which is generally less than about 1 micron, often less than about 100 m
• Many polymers of this type are disclosed in U.S. Pat. 3,142,568, issued July 28, 1964.
• a preferred class of vinyl polymers which can be employed in the practice of this invention are Water-insoluble interpolymers of acrylates or methacrylates with acrylic acid and a sulfobetaine having the formula:
• R, R and R are each hydrogen or alkyl and R and R are each divalent saturated hydrocarbon radicals, desirably containing up to 12 carbon atoms.
• Suitable sulfofetaine monomers include, for example, 5,5,l-trimethyl 9 oxo 8 oxa 5 azonia-lO-undecene-l-sulfonate, 4 t butyl 9 methyl 8 oxo 7 oxa-4-aza-9-decenel-sulfonic acid, 4,4,9 trimethyl 8-oxo-7-oxa-4-azonia-9- decene-l-sulfonate, and the like.
• the preferred polymers of this type contain, in polymerized form, at least 75%, preferably about 75 to about 93%, by weight, of acrylate or methacrylate, up to about preferably about 5 to about 15%, by weight, acrylic acid and up to about 10%, preferably about 2 to about 10%, by weight, of the sulfobetaine.
• a very convenient method for preparing the sulfobetaine monomers used in preparing the aforementioned preferred class of polymeric vinyl compounds comprises reacting the appropriate amino alkyl ester of an unsaturated carboxylic acid with the appropriate sultone.
• reaction can be carried out in the presence of an organic solvent such as acetonitrile, a liquid hydrocarbon or a ketone such as acetone at temperatures up to about 100" C., preferably 50 to about 80 C. In general, the reaction is complete in less than 8 hours, often in about 2 to about 6 hours. The reaction is not pressure dependent and therefore superatmospheric or subatmospheric pressures can be employed. The resulting sulfobetaine can be isolated by conventional procedures. The reactants are generally employed in stoichiometric concentrations although slight excesses of either reactant can be employed.
• reaction conditions for example, temperature, pressure, and the like, will depend upon the particular amino alkyl ester and sultone employed.
• Another class of polymeric vinyl compounds which is preferred in the practice of this invention is the interpolymers of; alkyl acrylates or methacrylates with sulfoesters having the formula: V
• alkyl radicals containing up to about l2 carbon atoms alkyl radicals containing up to about l2 carbon atoms
• R ' has its can be any aliphatic, cycloaliphatic or aromatic radical and will generally contain up .to about 12.carbon atoms.
• R radicals are alkylene radicals, generally those containing 2-4 carbons.
• R can also be a divalent aliphatic hydrocarbon radical in which there is a O- and/or -S- radical and generally contains up to 12 carbon atoms.
• Such R radicals can, therefore, be saturated or unsaturated, althoughsaturated.
• divalent alkylene groups in which the carbon chain is interrupted by oxygen and sulfur atoms are preferred.
• Suitable R radicals include, for example, ethylene 1,3- propylene, 1,2-propylene, tetramethylene,
• 1,3-isobutylene pentamethylene, hexamethylene, octamethylene, phen ylene, bisphenylylene, naphthylene, cyclopentylene, cyclo hexylene, Z-butenylene, butynylene, 2-oxatrimethylene, 3""
• M is a cation, as exemplified by hydrogen, an alkali metal such as sodium or potassium, ammonium, the cation of an organic'arnine such as 'triethyl amine, diethanol amine and the like.
• the sulfoesters can be preparedusing any method knownto be-suitable for thlSPUIPOSESpFOI example, U.S. Pat. 2,923,734, issued Feb. 2, 1960, discloses the preparation of such esters by the reaction of an a-methylene carboxylic acid with an aliphatic hydroxy sulfonic acid while U.S. Pat. 3,024,221, issued Mar. 6,- 1962, discloses a method forv preparing the sulfoester by reacting the appropriate acyl halide With the salt of the hydroxy sulfonic .lacid.
• hydroxy 'sulfonic acids examples include 2-hydroxyethane sulfonic acid, Z-hydroxy-l-propane sulfonic acid, l-hydroxy '2 butane sulfonic acid, 2-hydroxycyclohexane sulfonic acid, p-phenolsulfonicacid,
• u-Methylene carboxylic acids or acyl halides include acrylic acid, methacrylic acid, tit-butylacrylic acid, acyloyl chloride, methacryloyl bromide, ochexylacryloyl chloride and the like.
• the preferred class of polymers of the sulfoesters generally contains, in"
• polymeric form at least 65%,prefera'bly about to about by Weight, of the alkyl acrylate' or meth-- acrylate and up to about 15%, preferably about 5 to I about 15%,by weight, of the sulfoester.
• the temperature at -which the polymeric vinyl prepared is subject to-Wide variation since this temperacom pounds employed in the practice of this'invention are ture depends upon such variable: features as'the specific monomer used, duration of heating; pressureemployed andlike considerations. However; the polymerization" temperaturegenerall'y does not exceed about- C., r
• Thepoly'merization can be carried outin suitable" solvents or diluents, for example, wate'r or'frnixturesof water with' water miscible solvents, as-exemplifie'd by" methanol, "ethanol,” propanol, -isopr'opyl* alcohol, "fbutyl 1 alcohol, and the like.
• suitable solvents or diluents for example, wate'r or'frnixturesof water with' water miscible solvents, as-exemplifie'd by" methanol, "ethanol,” propanol, -isopr'opyl* alcohol, "fbutyl 1 alcohol, and the like.
• the pressure employed in the polymerization "if any, usually only sufiicieutto'rnain'.
• the free radical catalysts such as hydrogen peroxide, cumene hydroperoxide, water soluble azo type initiators and the like.
• the usual ingredients can be employed.
• the polymer can be isolated from the reaction vehicle by freezing, salting out, coagulation or by using other separation procedures suitable for this purpose.
• the photographic silver halide can be dispersed in the binding agent in a variety of ways, for example, an aqueous dispersion of the photographic silver halide in hydrophilic colloid, preferably gelatin, can be mixed with an aqueous dispersion of the polymeric vinyl compound. Alternatively, the photographic silver halide can be precipitated in an aqueous dispersion of the polymeric vinyl compound and hydrophilic colloid. In this case, a Water soluble silver salt such as silver nitrate is admixed with the silver halide such as potassium bromide in the presence of the mixture.
• the photographic silver halide is precipitated in hydrophilic colloid, e.g., an aqueous gelatin solution, and digested in the conventional manner known to the art. After digestion, but prior to coating, there is added to the emulsion an aqueous dispersion of the polymeric vinyl compound. The bulk of the resulting dispersion can be increased by the addition of more of the polymeric vinyl compound and/or natural or synthetic colloid or other binding material suitable for use in photographic silver halide emulsions. l
• the hydrophilic colloid which constitutes one com ponent of the binding agent for the photographic silver halide emulsion described herein is preferably gelatin.
• the binding agent can also comprise other binding materials such as natural and/ or synthetic water soluble polymers, particularly water soluble vinyl polymers, as exemplified by mono and polysaccharides, cellulose derivatives, proteins, water soluble polyacrylamides, polyvinyl pyrrolidones, and the like.
• the bind ing agent comprises a mixture of polymeric vinyl compound, in a concentration in the range of about 20 to about 80 percent, by weight, with the remainder of the binding agent being gelatin.
• Typical hydrophilic colloids that can be used in the binding agent include for example, gelatin, colloidal albumin, cellulose derivatives, synthetic resins, for example, polyvinyl alcohol, acrylamide polymers, and the like.
• any of the photographic silver halides can be used in the preparation of the fogged, direct-positive photographic silver halide emulsions employed in the practice of this invention as exemplified by silver bromide, silver chlorobromoiodide, silver chlorobromide, silver chloride and the like.
• the photographic silver halide emulsions can be lithographic silver halide emulsions in which the halides generally comprise a mixture of chloride and bromide.
• Such high contrast emulsions preferably contain less than mole percent iodide.
• photographic silver halide emulsions can contain silver halide grains which form latent images predominantly on the surface of the grains or those which form latent images predominantly inside the silver halide crystals, as exemplified by those described in Davey and Knott U.S. Pat. 2,592,250, issued Apr. 8, 1852, Luckey and Hoppe U.S. Pat. 2,996,302, issued Aug. 15, 1961, and Luckey and Hoppe U.S. Pat. 3,178,282, issued Apr. 13, 1965.
• the preferred photographic emulsions are those which have high internal sensitivity and low surface sensitivity.
• the fogging ofthe photographic emulsions used in the, practice of this invention can be effected using any method suitable for this purpose.
• such fogging can be accomplished by exposing the emulsion to light as described in Shirk U.S. Pat. 2,944,897, issued July 12, 1960.
• Other methods such as chemical fogging methods can also be used.
• fogging can be effected by chemical sensitization to fog using chemical sensitizing agents such as gold or noble metal sensitizers, sulfur sensitizers such as labile sulfur compounds and the like.
• the emulsions can also be fogged by treating with reducing agents such as formaldehyde, stannous chloride, thiourea dioxide and the like as described, for example, in Hillson U.S. Pat. 3,062,651, issued Nov. 6, 1962.
• the fogging is generally sufficient to give a density of at least 2.0 when the coated emulsion is processed in a photographic developer.
• Typical supports are the flexible supports of materials such as metal, paper, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyolefin film, polycarbonate film, polyethylene terephthalate or other polyester film and other related materials.
• Supports such as paper which are partially acetylated or coated with an a-olefin polymer, particularly a polymer of an oc-Olefin containing 2-10 carbon atoms, as exemplified by polyethylene, polypropylene, ethylene butene copolymers and the like, give good results.
• Photographic silver halide emulsion layers and other layers present in the photographic elements made according to the invention can be hardened with any suitable hardeners such as aldheyde hardeners, aziridine hardeners, hardeners which are derivatives of dioxane, oxy polysaccharides, such as oxy starch, oxy plant gums and the like.
• the photographic emulsions can also contain additional additives, particularly those known to be beneficial in photographic emulsions, including for example, stabilizers, particularly the water soluble inorganic acid salts of cadmium, cobalt, manganese and zinc such as disclosed in U.S. Pat. 2,829,404, the substituted triazaindolizines as disclosed in U.S. Pat.
• spectral sensitizers such as the cyanines, merocyanines, complex (trinuciear) cyanines, complex (trinuclear)merocyanines, styryls, hemicyanines, speed increasing materials, plasticizers, absorbing dyes, and the like.
• coating aids can also be used in the photographic emulsions. Typical coating aids are the anionic, nonionic and amphoteric surface active compounds.
• onium salts such as quaternary ammonium salts, sulfonium salts and phosphonium salts
• onium salts such as quaternary ammonium salts, sulfonium salts and phosphonium salts
• quaternary ammonium salts include nonyl pyridinium perchlorate, hexoxymethyl pyridinium perchlorate, ethylene bis-dioxymethyl pyridinium perchlorate and others described by Carroll U.S. 2,271,623, issued Feb. 3, 1942, hexadecamethylene-l,l6-bis(pyridinium perchlorate), 9 16 diaza-7,18-dioxa-8,17-dioxotetracosane-,
• EXAMPLE 1 When a binding agent comprising a hydrophilic colloid and a polymerized vinyl compound is employed in a fogged, direct-positive photographic silver halide layer there is a reduction in D loss upon deformation. Furthermore, polymerized vinyl compounds prepared from alkyl acrylates and sulfobetaine monomers are particularly eifective in practicing this invention. To illustrate, a latex of copoly(n-buty1 acrylate-acrylic acid-4,4,9 trimethyl-8-oxo-7-oxa-4-azonia-9-decene-l-sulfonate) is prepared in the following manner: A solution of 12.2 g. (0.10 mole) of 1,3-propane sultone and 15.7 g.
• the sulfobetaine monomer is copolymerized with alkyl acrylate and acrylic acid to form the polymerized vinyl compound using the following procedure: 375 ml. of distilled water is placed in a flask, heated to 80 C. and degassed with nitrogen. Then 3.9 ml. of Triton 770 (40% solution), 1.5 g. of potassium persulfate and 0.5 g. of sodium bisulfite are added in the order given. After the additions, the following two solutions are added under nitrogen with vigorous stirring over 12 minutes: 1) a solution of 138.6 g. of n-butyl acrylate and 15.4 g. of acrylic acid and (2) 3.9 m1. of Triton 770 (40% solution) and 12.5 g.
• the emulsion is coated on conventional cellulose acetate film base at a coverage of 308 mg. of silver per square foot and 306 mg. of gelatin per square foot without copolymer (Coating A-Control), With 39.4 g. of copolymer per mole of silver halide (Coating B) and with 65.6 g.
• Coating C copolymer per mole of silver halide
• the coatings are subjected to the deformation test described hereinabove, exposed in an Eastman IB sensitometer, developed for 2% minutes in Kodak Developer D-85, fixed, washed
• Tripleton 770 is a surfactant composition composed of a sodium alkyl aryl polyether sulfate and isopropanol, manufactured by Rohm and Haas C0.
• EXAMPLE 2 A latex of copoly(methyl acrylate-sodium 4-acryloyloxybutane-Z-sulfonate) (:5 Weight percent) is prepared in the following manner: 375 ml. of distilled water is placed in a flask, heated to 95 C. and purged of oxygen by bubbling in nitrogen. To the water is added 4 ml. of Triton 770 (40% solution), 1.0 g. of potassium persulfate and 0.1 g. of sodium bisulfite. The following monomer and solution are then added simultaneously under nitrogen with vigorous stirring over a period of 15 minutes: (1) 118.7 g. of methylacrylate and (2) a solution of 6.3 g.
• copolymer prepared using the above procedure is incorporated into the fogged, direct-positive photographic silver halide emulsion layer of Example 1 using the procedure described in that example.
• Coating A is the control and contains no copolymer while Coating B contains 59.5 grams per mole of silver halide of copolymer.
• EXAMPLE 3 As already indicated, the concentration of polymerized vinyl polymer in the binding agent is subject to variation.
• copoly(methyl acrylate-sodium-4-acryloyloxypropane-Z-sulfonate) (95.5 weight percent) is prepared using the polymerization procedure of Example 2 with sodium-4-acryloyloxypropane-2-sulfonate. 59.5 g. of the copolymer per mole of silver halide is incorporated into the fogged, direct-positive photographic silver halide emulsion of Example 1 which is coated using the procedure in Example 1, except that the gelatin coverage is reduced to mg. of gelatin per square foot.
• Coating A contains no additional copolymer and Coating B contains 59.5 g. of copolymer per mole of silver halide.
• the binding material employed in the practice of this invention can contain other hydrophilic colloids, particularly water soluble polymers such as polyacrylamides, in combination with gelatin.
• the procedure of Example 1 is repeated using'a binding material comprising a water soluble polyacrylamide prepared according to the procedure of Minsk et al. UN.S. Pat. 2,486,191, issued Oct. 25, 1949, gelatin and copoly(methyl acrylate-sodium-4-acryloyloxypropane- 2-sulfonate) of Example 3 (Coating B) or copoly(n-butyl acrylate acrylic acid) of Example 4 (Coating C).
• the emulsion is coated on conventional polyester film base at a coverage of 412 mg. of silver per square foot. After exposure, development and processing as in Example 1 the loss in D upon deformation is as follows:
• EXAMPLE 6 As already indicated, water-soluble polymerized vinyl compounds such as polyacrylamide are not effective to reduce loss in D when employed as one component of the binding agent according to the practice of this invention. To illustrate, 65.6 g. and 96.0 g. of water-soluble polyacrylamide prepared according to the procedure described in Minsk et al. US. Pat. 2,486,191, issued Oct. 25, 1949, are incorporated into separate coatings of the fogged, direct-positive photographic silver halide emulsion layer of Example 1 using the procedure described in that example.
• each coating exhibits a D loss of 4, indicative of a severe loss in D
• a means for reducing the loss in D exhibited by fogged, direct-positive photographic silver halide emulsion layers upon physical deformation
• a fogged, direct-positive, photographic silver halide emulsion having high internal sensitivity and low surface sensitivity in which the binding agent comprises gelatin and an aqueous dispersion of water-insoluble alkyl acrylate polymer, said binding agent comprising about 20 to about 80%, by weight, of said alkyl acrylate polymer, based on the combined weight of gelatin and alkyl acrylate polymer.
• a photographic element comprising a support and at .least one fogged, direct-positive, photographic silver halide emulsion layer having a binding agent comprising a hydrophilic colloid and water-insoluble polymerized vinyl compound in which the binding agent for the emulsion layer comprises about 20 to about 80%, by weight, of polymerized vinyl compound based on the combined weight of hydrophilic colloid and water-insoluble polymerized vinyl compound.
• polymeric vinyl compound is a copolymer of an alkyl acrylate with a monomer having the formula:
• R is hydrogen or alkyl
• R has its valence bonds on diiferent carbon atoms and is a divalent hydrocarbon radical or a divalent aliphatic hydrocarbon radical in which the chain of carbon atoms joining the oxygen and sulfur atoms of the above formula is interrupted by an oxygen or sulfur atom and M is a cation.
• polymeric vinyl compound is a copolymer of an alkyl 11 acrylate with acrylic acid and a monomer having the formula:
• R, R and R are each hydrogen or alkyl and R and R are each divalent saturated hydrocarbon radicals.
• hydrophilic colloid comprises gelatin and water soluble polyacrylamide.

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• 1965
  • 1965-11-08 US US506862A patent/US3512985A/en not_active Expired - Lifetime
• 1966
  • 1966-09-27 US US582262A patent/US3477852A/en not_active Expired - Lifetime
  • 1966-11-03 BE BE689233A patent/BE689233A/xx unknown
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