US3438779A - Mordants for bleachable filter layers - Google Patents

Mordants for bleachable filter layers Download PDF

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US3438779A
US3438779A US479718A US3438779DA US3438779A US 3438779 A US3438779 A US 3438779A US 479718 A US479718 A US 479718A US 3438779D A US3438779D A US 3438779DA US 3438779 A US3438779 A US 3438779A
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Donald W Heseltine
Dugald A Brooks
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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

  • This invention relates to certain bulky, i.e., relatively high molecular weight, quaternary nitrogen heterocyclic compounds which function as alkali-release mordants, to photographic materials and more particularly to photographic elements containing these compounds in lightscreening and light-absorbing layers, and to methods for their preparation.
  • 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 antihalation 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 ineffective, i.e., decolorized or destroyed and removed prior to or during or after photographic processing. For many purposes it is particularly convenient to employ lightscreening substances which are rendered ineffective by oneof the photographic baths employed in processing the element after exposure, such as a photographic developing bath or fixing bath.
  • 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.
  • an object of the invention to pro vide a photographic element having one or more layers containing at least one of the bulky nitrogen heterocyclic compounds or salts of the invention described above. Another object is to provide a backing layer containing at least one of these salts. Another object is to provide a light filter layer containing at least one of the above salts; which layer may be coated between two or more silver halide emulsion layers in a multilayer element. Another object is to provide an imbibition blank containing at least one of the above salts. Another object is to provide a light-sensitive gelatino-silver halide layer containing at least one of the above salts. Another object is to provide overcoating layers for photographic elements which contain at least one of the above salts. Another object is to provide a process for preparing the bulky quaternary nitrogen heterocyclic compounds and salts thereof. Other objects will become apparent from consideration of the description and the examples.
  • the bulky quaternary nitrogen heterocyclic compounds of the invention that are useful as alkali-release mordants include those represented by the following general formula:
  • R and R each represents the hydrogen atom, an alkyl group of from 1 to 18 carbon atoms and preferably a lower alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, hexyl, dodecyl, octadecyl, benzyl, phenethyl, etc.), or an aryl group (e.g., phenyl, tolyl, naphthyl, etc., and preferably phenyl), R represents a divalent alkylene group containing up to about 18 carbon atoms in the chain (e.g., methylene, ethylene, propylene, 1,2-propylene, butylene, hexatmethylene, decamethylene, octadecamethylene, Xylylene, etc.) or a divalent arylene group (e.g., p-phenylene,
  • a benzothiazole nucleus e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazo1e, 7-chlor0benzothiazole, 4-methylbenzothiazole, S-methylbenzothiazole, 6-methylbenzothiazole, S-bromobenzothiazole, 6-bro.mobenzothiazole, 4-phenylbenzothiazole, S-phenylbenzothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole, 6-methoxybenzothiazole, S-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, S-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, S-hydroxybenzothiazole
  • a naphthothiazole nucleus e.g., a-naphthothiazole, ,8-naphthothiazole, S-methoxy-fi-naphthothiazole, 5-ethoxy-B-naphthothiazole, 7-methoxy-a-naphthothiazole, 8-methoXy-u-naphthothiazole, etc.
  • a thianaphtheno-7',6',4,5-thiazole nucleus e.g., 4-methoxythianaphtheno-7,6',4,5-thiazole, etc.
  • an oxazole nucleus e.g., 4-rnethyloxazole, S-methyloxazole
  • a benzoxazole nucleus e.g., benzoxazole, S-chlorobenzoxazole, S-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, S-methoxybenzoxazole, 5-ethoxybenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, S-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.
  • a naphthoxazole nucleus e.g., ot-naphthoxazole, [Lfl-naphthoxazole, fl-naphthoxazole, etc.
  • a selenazole nucleus e.g., 4-methylselenazole, 4-phenylselenazole, etc.
  • a benzoselenazole nucleus e.g., benzoselenazole, 5-chloroselenazole, 5-methoxybenzoselenazole, S-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.
  • a naphthoselenazole nucleus e.g., ot-naphthoselenazole, fifi-naphthoselenazole, B-naphthoselenazole, etc.
  • a thiazolin nucleus e.g., thiazoline, 4-methylthiazoline, etc.
  • a quinoline nucleus e.g., quinoline, 3-methylquinoline, S-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.
  • an isoquinoline nucleus e.g., isoquinoline, B-methylisoquinoline, S-methylisoquinoline, 6-chloroisoquinoline, 6-methoxyisoquinoline, S-hydroxyisoquinoline, etc.
  • a 3,3-dialkylindolenine nucleus e.g., 3,3-dimethy1indolenine, 3,3,S-trimethylindolenine, 3,3,7-trimethylindolenine, etc.
  • a pyridine nucleus e.g., pyridine
  • imidazole nucleus e.g., imidazole
  • a benzimidazole nucleus e.g., benzimidazole, l-alkylbenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, etc.
  • a naphthimidazole nucleus e.g., 1-alkyl-a-naphthimidazole, 1-aryl-fl-naphthimidazole, 1-alkyl-5-methoxy-u-naphthimidazole, etc.
  • a thiazole nucleus e.g.,
  • an oxadiazole nucleus e.g., 1,2,4-oxadiazole,
  • a l or 4 alkyl-1,2,4-triazole nucleus e.g., l-methyl-l,2,4-triazole, l-butyl-l,2,4triazole,
  • a tetrazole nucleus e.g., a tetrazole nucleus
  • the bulky quaternary nitrogen heterocyclic compounds of the invention that are especially suitable as alkali-release mordant in photographic layers include those represented by the following general formula;
  • R represents the hydrogen atom and a lower alkyl group (e.g., methyl, ethyl, etc.)
  • R represents the hydrogen atom, a halogen atom (e.g., bromine, chlorine, etc.), a straight or branched chain alkyl group of from 1 to 22 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, hexyl, dodecyl, octadecyl, etc.), an aryl group (e.g., phenyl, tolyl, naphthyl, etc.), an aralkyl group (e.g., benzyl, phenethyl, etc.), an alk
  • Typical diamines are ehylenediamine, propylenediamine, 1,2,- propylenediamine, hexamethylenediamine, dodecamethylenediamine, phenylenediamine, tolylenediamine, xylenediamine, etc.), in an inert organic solvent (e.g., benzene, toluene, etc.), in the molar proportions of about 2 moles of the compound of Formula III to each mole of the compound of Formula IV. Mixtures of two or more compounds coming under Formula III can be employed, if desired.
  • the reaction mixture is heated for one or more hours, cooled and the crystalline product which forms is filtered otT, washed with a nonsolvent (e.g., absolute ethyl alcohol), and recrystallized from, for example, acetic acid and ethyl alcohol.
  • a nonsolvent e.g., absolute ethyl alcohol
  • the above defined mordants of the invention function as alkali-release" mordants in photographic layers.
  • they form methylene bases with loss of positive charges on the nitrogen atoms, and also lose their ability to act as mordants, with release and subsequent removal of the mordanted dye from the system.
  • a major advantage of the above alkali-release mordants is, therefore, that the compounds do not retain either the previously mordanted dye or thiosulfate ion from the fixing bath, after processing, as do other compounds of similar mordanting ability, providing a neutral or mildly alkaline hypo bath is used.
  • the invention is further illustrated by the following examples describing the preparation and use of the mordanting compounds of the invention in photographic layers and elements.
  • This compound under alkaline conditions forms a methylene base with loss of the positive charge on the nitrogen.
  • This compound at a ratio of 5 parts by weight to 1 part by weight of dye, mordanted the dye bis [3 methyl-l-p-sulfophenyl-2-pyrazolin-5-one-(4)]pentamethineoxonol, in gelatin, with no bleeding of the dye upon Washing in water.
  • the mordanted dye was partially bleached upon treatment of the coated gelatin layer (on a cellulose acetate film support) with a photographic developer having the composition:
  • the bleaching was increased when alkalinity of the developer was increased by the addition of sodium hydroxide.
  • a sample was treated with a fixing bath of the following composition:
  • the bleed test consisted of immersing a portion of the hand coating in stagnant, distilled water at F. for 2 minutes and inspecting for signs of dye bleeding out of the gel layer. If no bleeding was detected, the immersion was repeated for another 2 minute interval. Bleachability was determined by immersing a portion of the hand coating in the developer for 2 minutes and observing the loss in color. Bleachability in the fixing bath was also determined, but none of the above samples bleached under these conditions. Thiosulfate retention values were determined by the Ross-Crabtree method on unexposed film coatings, processed in a commercial Recordak processing machine.
  • Suitable intermediates include 2-methyl-4,6- di-m-(and p)tolylpyrylium halides, 4-methoxy-2,6-dimethylpyrylium halides, 2,4,6-trimethylpyrylium perchlorate, 2,6-dimethyl-4-(3-pyridyl)pyrylium halides, and the like, which are reacted with a diamine such as 1,6-hexamethylene diamine, in accordance with the process of the above example.
  • a diamine such as 1,6-hexamethylene diamine
  • alkali release mordants are used to advantage to form non-diffusing salts with light-filtering acid dyes that are valuable for use in photographic elements.
  • the photographic elements prepared with the above described 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 light-sensitive 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 support 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.
  • the colloidal binder material For most purposes, it is also desirable to add agents to harden the colloidal binder material so that the lightscreening layer will remain intact in the photographic element during and following the processing operations.
  • 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.
  • the proportions of mordant, dye, colloidal binder, hardener and coating aid may be varied over wide ranges and will depend upon the specific requirements of the photographic element being produced. The methods used to determine the optimum compositions are well known in the art and require no further elucidation here.
  • 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 US. Patent 2,949,442, issued Aug. 16, 1960, polyvinyl alcohol, polyvinyl pyrrolidone, and others well known in the art.
  • the abovementioned amphoteric copolymers are made by polymerizing the monomer having the formula:
  • R represents an atom of hydrogen or a methyl group, and a salt of a compound having the general 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, acryla-mide, methacrylamide, etc.
  • Examples of these polymeric gelatin substitutes are copolymers of allylamine and and more particularly the dyes of the formula:
  • n in each case is an integer of from 1 to 3
  • 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 benzoXaZole-pyrazolone merocyanine dyes described in copending application of Jones et al. US. Ser. No. 167, 666, filed Jan. 22, 1962, now Patent No. 3,282,- 699, 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 hereocyclic 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 benzoxazole series which has a sulfo-substituent on the benzene ring as well as one or more
  • 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(1- butyl-3-carboxymethylhexahydro-2,4,6-trioxo 5 pyrimidine)-pentamethineoxonol, bis(l car'boxymethyl 3- cyclohexylhexahydro-2,4,6-trioxo 5 pyrimidine) pentamethineoxonol, bis(1-butyl 3 carboxymethylhexahydro-2,4,6-trioxo 5 pyrimidine)trimethineoxonol, bis(1- carboxymethylhexahydro 3 octyl-2,4,6-trioXo--pyrimidine)methineoxonol, 4-[(3 ethyl-2-(3H)-benzoxazolylidine)-ethylidene]-3-methyl-1-(p-sulfophenyl) 2 pyrazolin-5-one monosulfonated
  • Patent 2,739,888 issued Mar. 27, 1956, such as 3-phenyl-2-phenylimino-S-o-sulfobenzal-4-thiazolidone sodium salt, 5-(4- methoxy-3-sulfobenzal)-3-phenyl-2-phenylimino 4 thiazolidone (sodium salt), 3-phenyl-2-phenylamino-5-[3-sul fobenzamido)-benzal] 4 thiazolidone (sodium salt), 3- benZyI-Z-phenylimino-5-o-sulfobenzal-4-thiazolidone (sodium salt), 5-(2,4-dicarboxymethoxybenzal)-3-phenyl-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 mucobr'omic 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 chloride such as terephthaloyl chloride or naphthalene1,5-disulfonyl chloride as described in Allen and Carroll U.S.
  • hardening agents as formaldehyde
  • a halogen-substituted aliphatic acid such as mucobr'omic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937
  • the photographic element utilizing our 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.
  • FIG. 1 shows a light screening layer 10 comprising gelatin, an acid substituted filter dye and the mordant of the Example 1 coated over a light-sensitive silver halide emulsion layer 11 which is coated on support 12.
  • FIG. 2 shows antihalation layer 15 comprising gelatin, an acid substituted dye and the mordant of the Example 1 coated adjacent to support 16 and a light-Sensitive silver halide emulsion layer 14 coated over layer 15.
  • FIG. 3 shows a multilayer color element comprising a support 21 having a red-sensitive silver halide emulsion layer 20 coated thereon, a green-sensitive silver halide emulsion layer 19 coated over layer 20, a lightscreening layer 18 comprising gelatin, an acid substituted dye of the Example 1 coated over layer 19, and a bluesensitive silver halide emulsion layer 17 coated o-ver layer 18.
  • 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.
  • the subject mordants are advantageously incorporated in photographic layers in a wide range of concentrations suitable to mordant acid dyes in the layer, such mordant concentrations being substantially higher than the amounts of addenda commonly used in photographic emulsion layers to achieve sensitizing elfects.
  • An element comprising a support material having thereon a hydrophilic colloid layer containing at least one salt of a water-soluble acid dye and a mordant compound having the formula:
  • a light-sensitive photographic element comprising a support material having thereon a hydrophilic colloid layer containing at least one substantially non-diifusible salt of a water-soluble acid dye with a compound of the wherein a. represents an integer of from 1 to 3, p represents an integer of from 1-18, R and R each represents a member selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group, with the --CHR R groups being substituted on a carbon atom, selected from the carbon atoms in the class consisting of the carbon atom in the 2 position and in the 4 position of the pyridinium ring, R represents a member selected from the class consisting of the hydrogen atom and a lower alkyl group, R represents a member selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkaryl group, an alkoxy group, an alkoxyalkyl group, an aryloxy group, a 2-thi
  • a light-sensitive photographic element comprising a support material having thereon at least two hydrophilic colloid layers, at least one of said hydrophilic colloid layers being a light-sensitive silver halide emulsion layer and at least one of said hydrophilic layers containing at least one non-difiusible salt of a water-soluble acid dye with a compound of the formula:
  • GEE-31 wherein d represents an integer of from 1 to 3, p represents an integer of from 1-18, R, and R each represents a member selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group, with the CHR R groups being substituted on a carbon atom selected from the carbon atoms in the class consisting of the carbon atom in the 2 position and in the 4 position of the pyridinium ring, R represents a member selected from the class consisting of the hydrogen atom and a lower alkyl group, R represents a member selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkaryl group, an alkoxy group, an alkoxyalkyl group, an aryloxy group, a halogen atom, a Z-thienyl group, a 2-pyr1yl group, a 2-indolyl group, a 3-indolyl group, a Z-fury
  • a light-sensitive photographic element comprising a support-material having coated thereon at least one light sensitive silver halide emulsion layer and having coated over said emulsion layer a hydrophilic colloid layer containing at least one substantially non-difiusible salt of a water-soluble acid dye with a mordant compound of the formula:
  • R represents a member selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group, with the -CH R goups being substituted on a carbon atom, selected from the carbon atoms in the class: consisting of the carbon atom in the 2 position and in the 4 position of the pyridinium ring
  • R represents a member selected from the class consisting of the hydrogen atom and a lower alkyl group
  • R represents a member selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkaryl group, an alkoxy group, an alkoxyalkyl group, an aryloxy group, a halogen atom, a 2-thienyl group, a Z-pyrryl group, a 2-indolyl group, a S-indolyl group, a Z-furyl group, a 3-pyridyl group, and a 4-pyridyl group,
  • a photographic element of claim 2 wherein said compound is 1,6-heXamethylene-bis(2-rnethyl-4,6-diphenylpyridinium iodide).
  • a light sensitive photographic element wherein at least one of said dy'e components of said salts is a dye selected from the group consisting of 4 [(3 ethyl 2(3H) benzoxazolylidene)ethylideneJ- 3 methyl 1 p sulfophenyl 2 pyrazolin 5 one monosulfonated, bis(1 butyl 3 carboxy-methyl 5- barbituric acid)trimethineoxonol, 4-[4-(3-ethyl-2(3H)- benzoX-azolylidene) 2 butenylidene] 3 methyl 1- p sulfophenyl 2 pyrazolin 5 one monosulfonated, bis(1 butyl 3 carboxyrnethyl 5 barbituric acid) pentamethineoxonol, bis[3 methyl 1 (p sulfophenyl) 2 pyrazolin 5 one (4)]methineo
  • a light-sensitive photographic element wherein at least one of said dye components of said salts is a dye selected from the group consisting of 4 [(3 ethyl 2(3H) benzoxazolylidene)ethylidene]- 3 methyl 1 p sulfophenyl 2 pyrazolin S one monosulfonated, bis(1 butyl 3 carboxy methyl 5- barbituric acid) trimethineoxonol, 4-[4-(3-ethyl-2(3H)- benzoxazolylidene) 2 butenylidene] 3 methyl 1 psulfophenyl 2 pyrazolin 5 one monosulfonated, bis[l butyl 3 carboxymethyl 5 b-arbituric acid) pentamethineoxonol, bis[3 methyl l (p sulfophenyl)- 2 pyrazolin 5 one (4)]methineoxonol
  • a photographic element comprising a support materral having thereon a hydrophilic colloid layer containmg at least one salt of a water-soluble acid dye and a mordant compound having the formula:
  • R and R each represents a member selected from the class consisting of the hydrogen atom, a lower alkyl group, and an aryl group
  • R represents a member selected from the class consisting of a divalent alkylene group, a phenylene group, a tolylene group and a xylylene group
  • X reperesents an acid anion
  • Z and Z each represents the nonmetallic atoms necessary to complete a 5 to 6 membered heterocyclic nucleus selected from the class consisting of a thiazole nucleus, at benzothiazole nucleus, 21 naphthiazole nucleus, a thianaphtheno-7',6',4,5-thiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole

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  • Plural Heterocyclic Compounds (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)
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US479762A Expired - Lifetime US3455693A (en) 1965-08-16 1965-08-16 Mordants for use in dyed filter layers
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US4424272A (en) 1981-08-03 1984-01-03 Polaroid Corporation Temporary polymeric mordants and elements containing same
EP0772080A2 (en) 1995-11-02 1997-05-07 Eastman Kodak Company Photographic element useful as a motion picture print film

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GB1528616A (en) * 1975-06-04 1978-10-18 Ciba Geigy Ag Alkali-release mordants
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
US5244994A (en) * 1992-03-20 1993-09-14 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
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

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US3016306A (en) * 1957-11-25 1962-01-09 Eastman Kodak Co Yellow filter layers for multi-layer photographic color elements
US3271148A (en) * 1962-07-19 1966-09-06 Eastman Kodak Co Mordanting of acid dyes

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US2675316A (en) * 1949-04-14 1954-04-13 Eastman Kodak Co Photographic elements containing mordants
US2595225A (en) * 1950-02-09 1952-05-06 Du Pont Polymeric poly-quaternary ammonium salts
BE543031A (enrdf_load_stackoverflow) * 1954-12-29
US2972537A (en) * 1957-09-03 1961-02-21 Eastman Kodak Co Condensation products of polyvinylketones with hydrazides containing quaternary nitrogen groups
FR1361293A (fr) * 1962-07-19 1964-05-15 Kodak Pathe Nouvelle composition de mordançage utilisable notamment en photographie

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Publication number Priority date Publication date Assignee Title
US3016306A (en) * 1957-11-25 1962-01-09 Eastman Kodak Co Yellow filter layers for multi-layer photographic color elements
US3271148A (en) * 1962-07-19 1966-09-06 Eastman Kodak Co Mordanting of acid dyes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4424272A (en) 1981-08-03 1984-01-03 Polaroid Corporation Temporary polymeric mordants and elements containing same
EP0772080A2 (en) 1995-11-02 1997-05-07 Eastman Kodak Company Photographic element useful as a motion picture print film

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US3444138A (en) 1969-05-13
DE1547716A1 (de) 1970-03-05
GB1162214A (en) 1969-08-20
BE685292A (enrdf_load_stackoverflow) 1967-01-16
GB1151877A (en) 1969-05-14
DE1547724A1 (de) 1970-02-19
DE1547716B2 (de) 1976-09-23
CH494977A (fr) 1970-08-15
DE1295368B (de) 1969-05-14
US3425833A (en) 1969-02-04
CH483035A (fr) 1969-12-15

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