US3444138A - Mordants for bleachable filter layers - Google Patents

Mordants for bleachable filter layers Download PDF

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US3444138A
US3444138A US480111A US3444138DA US3444138A US 3444138 A US3444138 A US 3444138A US 480111 A US480111 A US 480111A US 3444138D A US3444138D A US 3444138DA US 3444138 A US3444138 A US 3444138A
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dye
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Jack L R Williams
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Eastman Kodak Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/10—Quaternary compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/04—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/84—Naphthothiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D293/00—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms
    • C07D293/02—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms not condensed with other rings
    • C07D293/04—Five-membered rings
    • C07D293/06—Selenazoles; Hydrogenated selenazoles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/835—Macromolecular substances therefor, e.g. mordants
    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/42—Structural details
    • G03C8/52—Bases or auxiliary layers; Substances therefor
    • G03C8/56—Mordant layers
    • 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
    • Y10S430/142—Dye mordant

Definitions

  • Such dye-mordant lightscreening salt may be in a layer overlying a light-sensitive emulsion or overlying two or more light-sensitive emulsions; or it may be in a light-sensitive emulsion for the purpose of modifying a light record in such emulsion or for protecting an overlying light-sensitive emulsion or emulsions from the action of light of wavelengths absorbed by such light-screening substance, or it may be in a layer not containing a light-sensitive substance but arranged between two light-sensitive emulsions; or it may be in a layer serving as a backing on an element having one or more light-sensitive emulsions (for example, to reduce halation).
  • light-screening substances are often required (a) in overcoatings upon photographic elements to protect the light-sensitive emulsion or emulsions from the action of light which it is not desired to record, (-b) in layers arranged between differentially color sensitized emulsions, e.g., to protect redand green-sensitive emulsions from the action of blue light, and (c) in backings forming the so-called anti-halation layers on either side of a transparent support carrying the light-sensitive emulsion or emulsions.
  • the element contains a color sensitized emulsion or color sensitized emulsions
  • light-screening substances which can readily be rendered inelfective, i.e., decolorized or destroyed and removed prior to or during or after photographic processing.
  • mordants Numerous substances have been proposed as mordants to prepare the dye-mordant salts used as light-screening and light-absorbing materials for the purposes indicated above.
  • the proposed mordants are relatively high molecular weight compounds having ionic charges opposite to those of the particular light-absorbing dye.
  • the dye employed might be an acid dye, in which case the mordant would be a cationic compound.
  • Typical of such proposed mordants are, for example, derived polymers such as the basic reaction products of polyvinylsulfonates and C-aminopyridines as described in D. D. Reynolds et al., US. Patents 2,701,243 and 2,768,078, granted Feb. 1, 1955, and Oct. 23, 1956, respectively.
  • hydrophilic materials such as gelatin and readily form substantially non-dilfusible salts with water-soluble acid dyes.
  • they have a molecular weight of about at least 300, although polymeric materials having a molecular weight of 600 to 50,000, and higher, have been found to be particularly useful in my invention.
  • an object of the invention to provide a new class of polymeric quaternary nitrogen heterocyclic compounds, and salts thereof with water-soluble acid dyes. Another object is to provide an imbibition blank containing at least one of the above salts. Another object is to provide a process for preparing the new class of compounds and salts. Other objects will become apparent from consideration of the description and examples.
  • the new class of polymeric quaternary nitrogen heterocyclic compounds of the invention include those represented by the following general formula:
  • R represents a linear polymeric structure, for example, an addition type polymer such as a polymer of a monoethylenically unsaturated polymerizable compound having periodically occurring groups of the structure:
  • a monoethylenically unsaturated polymer e.g., a polyvinyl ester or alkyl ketone, a polyisopropenyl ester or alkyl ketone
  • the said chain may also include units of vinyl alcohol, unquaternized vinyl ester or vinyl alkyl ketone
  • R represents the hydrogen atom, a lower alkyl group (e.g., methyl, ethyl, etc.), or a phenyl group
  • R represents the hydrogen atom, an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, hexyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.), a hydroxyl, a halogen (e.g., chlorine or bromine), or an aryl group (e.g., phenyl, tolyl, bi
  • benzothiazole nucleus e.g., benzothiazole
  • a thianaphtheno- 7',6,4,5-thiazole nucleus (e.g.,
  • an oxazole e.g., S-methyloxazole, 4-phenyloxazole,
  • benzoxazole nucleus e.g., benzoxazole
  • a naphthoxazole nucleus e.g., u-naphthoxazole, fl,,8-naphthoxazole, ,B-naphthoxazole, etc.
  • a selenazole nucleus e.g., 4-methylselenazole
  • benzoselenazole nucleus e.g., benzoselenazole
  • a naphthoselenazole nucleus e. g., u-naphthoselenazole, fiJi-naphthoselenazole, fl-naphthoselenazole, etc.
  • thiazoline nucleus e.g., thiazoline
  • a quinoline nucleus e.g., quinoline
  • an isoquinoline nucelus e.g., isoquinoline
  • a 3,3-dialkylindolenine nucleus e.g.,
  • a pyridine nucleus e.g., pyridine, Z-methylpyridine,
  • imidazole nucleus e.g., imidazole, l-alkyl imidazole,
  • a benzimidazole nucleus e.g., benzimidazole
  • a naphthimidazole nucleus e.g., 1-alkyl-a-naphthimidazole, l-aryl-fl-naphthimidazole, 1-alkyl-5-rnethoxy-u-naphthimidazole, etc.
  • a l or 4 alkyl-1,2,4-triazole nucleus e.g.,
  • a tetrazole nucleus e.g., tetrazole
  • the new class of quaternary nitrogen heterocyclic polymers of the invention include derived resinous copolymers consisting essentially of not less than 25% by weight of polymerized units of the general structure:
  • the remainder of the polymer molecule may be polymerized units of the structures:
  • N CR3 prepared, for example, by polymerizing monomeric vinyl chloromethyl ketone (Catch et al., J. Chem. Soc., 1948, p. 278) in a solvent such as dioxane at 60 C. in the presence of a polymerization catalyst, e.g., azo-bis-isobutyronitrile.
  • a polymerization catalyst e.g., azo-bis-isobutyronitrile.
  • the proportions of the heterocyclic tertiary amine of Formula V above can vary widely, but preferably it is employed in the reaction in excess of the stoichiometrically calculated quantity, for example, from about 1.2 to 5, or more equivalent moles.
  • the reaction is carried out in an inert reaction medium which is a solvent for the starting polymer such as, for example, in acetone, dimethyl sulfoxide, N,N-dimethylformamide, 'y-butyrolactone etc.
  • the reaction mixture is allowed to stand for several days or more at room temperatures or heated for several hours.
  • the quaternary salt product which forms is isolated by precipitation into a nonsolvent for the salt product, or in the case where the salt product forms as a precipitate in the reaction mixture, the supernatant liquor can be simply decanted.
  • the quaternary salt product can then be further purified by washing with a non-solvent and dried preferably under vacuum.
  • the quaternary salt products consisting from about 25-100% by weight of quaternized units and from 75-0%, by weight of unquaternized residual units have been found to be especially efilcacious mordants in photographic layers and are preferred.
  • the photographic elements prepared with the abovedescribed polymeric and non-polymeric mordants of the invention comprise a support material having thereon at least one hydrophilic colloid layer containing a mordant of the invention, which layer may also contain a lightsensitive silver halide.
  • the preferred light-sensitive photographic elements comprise a support having thereon at least one hydrophilic colloid layer containing a mordant of the invention and at least one light-sensitive silver halide emulsion layer.
  • the mordant containing light-screening and antihalation layers are customarily prepared by coating on the sup ort or photographic element by methods well known in the art, a water solution comprising at least one mordant of the invention, an acid dye, a water permeable hydrophilic colloid binder and a coating aid such as saponin.
  • a water solution comprising at least one mordant of the invention, an acid dye, a water permeable hydrophilic colloid binder and a coating aid such as saponin.
  • the pH of the coating solution is adjusted when necessary to a level that is compatible with the light-sensitive emulsion layer by the usual methods.
  • Suitable support materials include any of those used in photography such as cellulose acetate, cellulose propionate, cellulose acetate-butyrate, cellulose nitrate, synthetic resins such as nylon, polyesters, polystyrene, polypropylene, etc., paper, and the like.
  • Suitable hydrophilic colloid materials that can be used in the mordant containing compositions and layers, and photographic elements, of the invention include gelatin, albumin, collodion, gum arabic, agar-agar, cellulose derivatives such as alkyl esters or carboxylated cellulose, hydroxy ethyl cellulose, carboxy methyl hydroxy ethyl cellulose, synthetic resins, such as the amphoteric copolymers described by Clavier et al. in U.S. Patent 2,949,442, issued Aug. 16, 1960, polyvinyl alcohol, polyvinyl pyrrolidone, and others Well known in the art.
  • the above-mentioned amphoteric copolymers are made by polymerizing the monomer having the formula:
  • R has the above-mentioned meaning, such as an alkylamine salt.
  • These monomers can further be polymerized with a third unsaturated monomer in an amount up to about 20 percent, and preferably from 5-15 percent, of the total weight of monomer used, such as an ethylene monomer that is copolymerizable with the two principal monomers.
  • the third monomer may contain either a basic group or an acid group and may, for example, be vinyl acetate, vinyl chloride, acrylonitrile, methacrylonitrile, styrene, acrylates, methacrylates, acrylamide, methacrylamide, etc.
  • polymeric gelatin substitutes examples include copolymers of allylamine and methacrylic acid; copolymers of allylamine, acrylic acid and acrylamide; hydrolyzed copolymers of allylamine, methacrylic acid and vinyl acetate; the copolymers of allylamine, acrylic acid and styrene; the copolymers of allylamine, methacrylic acid and acrylonitrile; etc.
  • the dyes that can be effectively mordanted in accordance with my invention include any filter dye that has one or more acidic group substituents such as sulfo or carboxyl groups, for example, the oxonol dyes described and claimed in copending application of Joseph Bailey, Ser. No. 98,709, filed Mar. 27, 1961, having the formula:
  • each R represents a carboxyalkyl group in which the carboxy substituent is attached to an alkyl group having from 1 to 2 carbon atoms
  • R is an alkyl group of from 1 to 8 carbon atoms or an aryl group such as phenyl or an alkyl or alkoxy substituted phenyl group
  • X is hydrogen or an alkyl group of from 1 to 4 carbon atoms, such that no more than one X is an alkyl group.
  • suitable acid dyes include the benzoxazolepyrazolone merocyanine dyes described in copending application of Jones et al. U.S. Ser. No. 167,666, filed J an. 22, 1962 having the formula:
  • R represents an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, etc., or a carboxyalkyl group, such as carboxymethyl, carboxyethyl, carboxypropyl, etc., or a sulfoalkyl group, such as sulfoethyl, sulfopropyl, sulfobutyl, etc.;
  • Z represents the nonmetallic atoms necessary to complete a heterocylic nucleus of the benzoxazole series (including benzoxazole and benzoxazole substituted with substitutions such as methyl, ethyl, phenyl, methoxy, ethoxy, chlorine, bromine, etc.) or a nucleus of the benzoxazoles series which has a sulfo-substituent on the benzene ring as well as one or more of
  • the invention is not limited to just those dyes coming within the general formulas of the above-mentioned copending applications, since as previously set forth any filter dye containing one or more sulfo or carboxyl groups can be employed.
  • any filter dye containing one or more sulfo or carboxyl groups can be employed.
  • Typical light-filtering dyes include, for example, bis(lbutyl 3 -carboxymethylhexahydro-2,4,6-trioxo-5-pyrimidine)-pentamethineoxonol, bis 1-carboxymethyl-3-cyclohexylhexahydro 2,4,6 trioxo-S-pyrimidine)pentamethineoxonol, bis(l butyl-3-carboxymethylhexahydro-2,4,6- trioxo 5 pyrimidine)trimethineoxonol, bis(l-carboxymethylhexahydro 3 octyl 2,4,6-trioxo-5-pyrimidine) meth'ineoxonol, 4 [(3 ethyl-2(3H)-benzoxazolylidine) ethylidene] 3 methylI-(p-sulfophenyl)-2-pyrazolin-5- one monosulfonated, 4-[4
  • Patent 2,739,- 888 issued Mar. 27, 1956, such as 3-phenyl-2-phenylimino-5-o-sulfobenZal-4 thiazolidone sodium salt, 5 (4- methoxy 3 sulfobenzal)-3-phenyl-2-phenylimino-4-thiazolidone (sodium salt), 3-phenyl-2-phenylimino-5-[3-(3- sulfobenzamido)benzal1-4-thiazolidone (sodium salt), 3- benzyl 2 phenylimino 5-o-sulfobenzal-4-thiazolidone (sodium salt), 5 2,4-dicarboxymethoxybenzal -3phenyl- 2-phenylimino-4-thiazolidone sodium salt, etc., tartrazine, and the like filter dyes.
  • Hardening materials that may be used to advantage include such hardening agents as formaldehyde; a halogen-substituted aliphatic acid such as mucobromic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937; a compound having a plurality of acid anhydride groups such as 7,8-diphenylbicyclo (2,2,2)-7- octene-2,3,5,6-tetra-carboxylic dianhydride, or a dicarboxylic or a disulfonic acid chlorine such as terephthaloyl chloride or naphthalene-1,5-disulfonyl chloride as described in Allen and Carroll US.
  • hardening agents as formaldehyde
  • a halogen-substituted aliphatic acid such as mucobromic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937
  • a compound having a plurality of acid anhydride groups such as
  • the photographic element utilizing my light-screening layers have light-sensitive emulsion layers containing silver chloride, silver bromide, silver chlorobromide, silver iodide, silver bromoiodide, silver chlorobromoiodide, etc., as the light-sensitive material. Any lightsensitive silver halide emulsion layers may be used in these photographic elements.
  • the silver halide emulsion may be sensitized by any of the sensitizers commonly used to produce the desired sensitometric characteristics.
  • My invention is further illustrated by the following examples describing the preparation of preferred mordants and the use thereof in photographic elements.
  • this product contained 2.8% by weight of nitrogen as compared with calculated theory of approximately 7% by weight of nitrogen for pure poly(vinyl pyridinium acetate) chloride. Accordingly, this derived polymer consisted essentially of about 40% by weight of recurring (vinyl pyridinium acetate) chloride units of the structure:
  • this derived polymer consisted essentially of about 49.8% by weight of recurring (vinyl pyridinium methyl ketone) chloride units of the structure:
  • EXAMPLE 3 To 1.0 cc. of 1 photographic gelatin melted at 40 C. was added 30 mg. of poly(vinyl pyridinium acetate) chloride dissolved in 10 cc. of water. The pH of the solution was adjusted to 4.5-5.0 with glacial acetic acid. To this was added 10 rngs. of bis[3-methyl-l-p-sulfophenyl-5- pyrazolone(4) ]pentamethene-oxonol dissolved in water with vigorous stirring. The pH of the melt was then readjusted to 60:0.1 with 2.5 N sodium hydroxide solution, a coating aid added, the total volume adjusted to 32 cc. with distilled water and the melt coated on a film support and dried.
  • Another portion of the coating was treated in a conventional alkaline silver halide developer solution containing hydroquinone and p-methylaminophenol sulfate as the developing agents.
  • the mordanted dye was completely bleached by this treatment.
  • the coating was treated in a conventional sodium thiosulfate fixing bath and then Washed. No residual sodium thiosulfate was detected in the coating by the Ross-Crabtree method.
  • EXAMPLE 4 This example shows the use of the :derived polymers of the invention as on ultraviolet absorbing overcoating layer over light-sensitive gelatino-silver halide emulsion layers, for example, over the emulsion layers of a multilayer color element of the type described in Mannes et al., US. Patent 2,252,718, issued Aug. 1 9, 1941.
  • a gelatin-mordant composition was prepared by mixing 200 g. of a 10% aqueous gelatin solution at 40 C. and 200 g. of a 15% aqueous solution of the polymeric mordant prepared according to Example .1(A) at 40 C. The clear solution obtained was then chilled, noodled, and washed with cold water in the normal manner for 6 hours, drained, remelted at 0 C. and (weighed.
  • a coating melt was then prepared as follows employing the above gelatin-mordant composition.
  • My alkali-release polymeric mordants are also used to advantage in mordanting light-filtering dyes, such as a blue-light absorbing dye having one or more acid substitutents, in a filtering layer between the top blue-sensitive layer and over the green-sensitive and the red-sensitive layers of a multilayer color photographic element of the type described in Mannes et al. US. Patent 2,252,7 1 8, referred to previously.
  • appropriate dyes of other colors can be used to advantage in mordanted filter layers between the green-sensitive and red-sensitive layers, or one or more appropriate dyes can be mord anted in an antihalation layer either between the light-sensitive layers and the support or on the side of the support away from the light-sensitive layers.
  • Examples 5 through 8 illustrate the use of the derived polymeric mordants of the invention in antihalation layers, and further illustrate the improvement obtained therewith in regard to hypo retention in the processed elements, as compared with an element prepared [with a known mordanting polymer and a non-mordanted control element.
  • the coating melts were prepared, in general, by the procedure described in above Example 4.
  • the melt compositions, with the exception of the control example, were coated on an ordinary cellulose acetate film support and over this melt layer was coated in each case a fine-grained silver chlorobromide gelatin emulsion layer.
  • the filter dyes employed are listed as follows:
  • EXAMPLE 6 A film element was coated having an antihalation undercoat comprising gelatin+poly(a-methylallyl-N-guanidyl-ketimine, glycolic acid salt) prepared in accordance with Minsk U.S. Patent 2,882,156, issued Apr. 14, 1959, as the mordant polymer (28 mg./ft. Dye A (2.4 mg./ ft. Dye B (1.6 mg./ft. Dye C (2.9 mg./ft and Dye D (2.5 mg./ft
  • EXAMPLE 7 A film element was coated having an antihalation undercoat comprising gelatin and the polymeric mordant of Example 1(A) (45 mg./ft. Dye A (2.4 mg./ft Dye B (1.6 mg./ft. Dye C (2.9 mg./ft. and Dye D (2.5 mg./ft.
  • EXAMPLE 8 A film element was coated having an antihalation undercoat comprising gelatin and the polymeric mordant of Example 1(A) (45 mg./ft. Dye E (5 mg./ft. Dye F (5 rug/ft?) and Dye G (5 mg./ft.
  • mordants are prepared according to the methods of the invention described in Examples 1 and 2 by reacting polyvinyl chloroacetate or poly(vinyl chloromethyl ketone) with the appropriate heterocyclic amine.
  • mordants of the invention can also be advantageously used in light-screening layers between two or more color sensitized silver halide emulsion layers, or in antihalation backing layers, or incorporated directly in light-sensitive silver halide emulsion layers, or they can be used to prepare imbibition dye transfer blanks of improved properties.
  • Z represents the atoms required to complete a nucleus selected from the class consisting of a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a thianaphtheno-7',6,4,5- thiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a thiazoline nucleus, a quinoline nucleus, an isoquinoline nucleus, a pyridine nucleus, an imidazole nucleus, 21 benzimidazole nucleus, a napththimidazole nucleus, a 3,3-dialkylindolenine nucleus, a 1,2,4-thiadiazole nu
  • m represents an integer of from 1 to 2
  • R represents a member selected from the class consisting of the hydrogen atom, a lower alkyl group and a phenyl group
  • R represents a member selected from the class consisting of the hydrogen atom, an alkyl group and an aryl group
  • X represents an acid anion
  • Z represents the nonmetallic atoms required to complete a heterocyclic nucleus selected from the class consisting of a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a thianaphtheno-7',6,4,5-thiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, 21 thiazoline nucleus, a quino
  • a resinous copolymer which functions as an alkalirelease mordant for acid dyes consisting essentially of from about 25100% by weight of recurring polymerized units of the structure:
  • m in each occurrence represents the same integer of from 1 to 2
  • R in each occurrence represents the same member selected from the class consisting of the hydrogen atom, a lower alkyl group and a phenyl group
  • X in each occurrence represents the same acid anion
  • R represents a member selected from the class consisting of the hydrogen atom, an alkyl group and an aryl group
  • Z represents the non-metallic atoms required to complete a heterocyclic nucleus selected from the class consisting of a thiazole nucleus, a benzothiazole nucleus, at naphthothiazole nucleus, a thianaphthen-7',6,4,S-thiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a
  • naphthoselenazole nucleus a thiazoline nucleus, a quinoline nucleus, an isoquinoline nucleus, a pyridine nucleus, an imidazole nucleus, a benzimidazole nucleus, a naphthimidazole nucleus, a 3,3-dialkylindolenine nucleus, a 1,2,4- thiadiazole nucleus, a 1,2,4-triazole nucleus, and a tetrazole nucleus.
  • a resinous copolymer which functions as a mordant for acid dyes consisting essentially of from about 25- 100% by weight vinyl pyridiniumacetate chloride units and from about 0% by weight of vinyl chloroacetate units.
  • a resinous copolymer which functions as a mordant for acid dyes consisting essentially of from about 25100% by weight of vinyl pyridiniummethyl ketone chloride units and from about 750% by weight of vinyl chloromethyl ketone units.
  • a non-sensitive element comprising a support material having thereon a hydrophilic colloid layer containing at least one compound of claim 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials Engineering (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Pyridine Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US480111A 1965-08-16 1965-08-16 Mordants for bleachable filter layers Expired - Lifetime US3444138A (en)

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US47972065A 1965-08-16 1965-08-16
US47976265A 1965-08-16 1965-08-16
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US479718A Expired - Lifetime US3438779A (en) 1965-08-16 1965-08-16 Mordants for bleachable filter layers
US479762A Expired - Lifetime US3455693A (en) 1965-08-16 1965-08-16 Mordants for use in dyed filter layers
US479720A Expired - Lifetime US3425833A (en) 1965-08-16 1965-08-16 Mordants for bleachable filter layers

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US479720A Expired - Lifetime US3425833A (en) 1965-08-16 1965-08-16 Mordants for bleachable filter layers

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BE (1) BE685292A (instruction)
CH (2) CH494977A (instruction)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4108802A (en) * 1975-06-04 1978-08-22 Ciba-Geigy Ag Quaternary ammonium polymers and photographic materials containing same
US4424272A (en) 1981-08-03 1984-01-03 Polaroid Corporation Temporary polymeric mordants and elements containing same
EP0561475A1 (en) * 1992-03-20 1993-09-22 Eastman Kodak Company Bleachable polymeric filter dyes
US5470986A (en) * 1994-06-27 1995-11-28 E. I. Du Pont De Nemours And Company Imidazolium hardeners for hydrophilic colloid

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3305978A1 (de) * 1983-02-21 1984-08-23 Siemens AG, 1000 Berlin und 8000 München Telekommunikationssystem mit abflachung von verkehrsspitzen
GB2140572B (en) * 1983-05-26 1986-06-18 Kodak Ltd Photographic dispersions
US5679505A (en) 1995-11-02 1997-10-21 Eastman Kodak Company Photographic element useful as a motion picture print film
EP0921435B1 (en) * 1997-12-02 2002-07-24 Tulalip Consultoria Comercial Sociedade Unipessoal S.A. Light-sensitive silver halide photographic elements containing yellow filter dyes
US6903475B2 (en) 2001-02-23 2005-06-07 Black & Decker Inc. Stator assembly with an overmolding that secures magnets to a flux ring and the flux ring to a stator housing
GB2552806A (en) * 2016-08-10 2018-02-14 Sumitomo Chemical Co Light filter and sensor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2595225A (en) * 1950-02-09 1952-05-06 Du Pont Polymeric poly-quaternary ammonium salts
US2972537A (en) * 1957-09-03 1961-02-21 Eastman Kodak Co Condensation products of polyvinylketones with hydrazides containing quaternary nitrogen groups

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2675316A (en) * 1949-04-14 1954-04-13 Eastman Kodak Co Photographic elements containing mordants
BE543031A (instruction) * 1954-12-29
CA633929A (en) * 1957-11-25 1962-01-02 Canadian Kodak Co. Limited Yellow filter layers for multi-layer photographic color elements
FR1361293A (fr) * 1962-07-19 1964-05-15 Kodak Pathe Nouvelle composition de mordançage utilisable notamment en photographie
BE634515A (instruction) * 1962-07-19

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2595225A (en) * 1950-02-09 1952-05-06 Du Pont Polymeric poly-quaternary ammonium salts
US2972537A (en) * 1957-09-03 1961-02-21 Eastman Kodak Co Condensation products of polyvinylketones with hydrazides containing quaternary nitrogen groups

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4108802A (en) * 1975-06-04 1978-08-22 Ciba-Geigy Ag Quaternary ammonium polymers and photographic materials containing same
US4424272A (en) 1981-08-03 1984-01-03 Polaroid Corporation Temporary polymeric mordants and elements containing same
EP0561475A1 (en) * 1992-03-20 1993-09-22 Eastman Kodak Company Bleachable polymeric filter dyes
US5470986A (en) * 1994-06-27 1995-11-28 E. I. Du Pont De Nemours And Company Imidazolium hardeners for hydrophilic colloid
US5591863A (en) * 1994-06-27 1997-01-07 Sterling Diagnostic Imaging, Inc. Imidazolium hardeners for hydrophilic colloids

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GB1163904A (en) 1969-09-10
US3438779A (en) 1969-04-15
US3455693A (en) 1969-07-15
DE1547724A1 (de) 1970-02-19
BE685292A (instruction) 1967-01-16
CH494977A (fr) 1970-08-15
DE1295368B (de) 1969-05-14
DE1547716A1 (de) 1970-03-05
DE1547716B2 (de) 1976-09-23
US3425833A (en) 1969-02-04
CH483035A (fr) 1969-12-15
GB1162214A (en) 1969-08-20
GB1151877A (en) 1969-05-14

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