US3425833A - Mordants for bleachable filter layers - Google Patents

Mordants for bleachable filter layers Download PDF

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US3425833A
US3425833A US479720A US3425833DA US3425833A US 3425833 A US3425833 A US 3425833A US 479720 A US479720 A US 479720A US 3425833D A US3425833D A US 3425833DA US 3425833 A US3425833 A US 3425833A
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Robert C Taber
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
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    • 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
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    • 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
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    • 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-halationlayers 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 light-screening substances which are rendered ineffective by one of 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.
  • 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 12 Claims al., US. Patents 2,701,243 and 2,768,078, granted Feb. 1, 1955, and Oct. 23, 1956, respectively.
  • Ibulky quaternary nitrogen heterocyclic compounds containing phenolic groups are especially useful as precipitants and mordants for acid dyes in photographic layers, and that these compounds satisfactorily overcome the above-mentioned shortcomings of heretofore known mordants for this purpose.
  • mordants are soluble in aqueous solutions, for example, dilute solutions of acids such as acetic, butyric, lauric, etc. acids.
  • they readily form substantially non-diffusable salts with water-soluble dyes, and these are all compatible with various hydrophilic materials such as gelatin. They are compounds of definite constitution and, in general, have molecular weights of about at least 300.
  • an object of the invention to provide 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 phenolic group containing bulky quaternary heterocyclic compounds that are useful as. alkali-release mordants include those represented by the following general formulas:
  • R represents the hydrogen atom, an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, hexyl, dodecyl,
  • an aryl group e.g., phenyl, tolyl, naphthyl, a phenolic group or ring such as p-hydroxyphenyh 4-hydroxy-3,i-dibromophenyl, 2 hydroxy-S-octylphenyl, S-hydroxynaphthyl, etc.
  • R represents an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, hexyl, dodecyl, etc.)
  • an aryl group e.g., phenyl, tolyl, naphthyl, a phenolic group or ring such as p-hydroxyphenyl, 4 hydroxy-3,S-dibrornophenyl, 2 hydroxy-S-octylphenyl, 4-hydroxynaphthyl, etc.
  • R and R each represents an alkyl group (e.g., methyl, e
  • a benzothiazole nucleus e.g., benzothiazole, 4-hydroxybenzothiazole, 4-chlorobenzothiazole, S-chlorob enzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, S-methylbenzothiazole, 6-methylbenzothiazole, S-bromobenzothiazole, 6-bromobenzothiazole, 4-phenylbenzothiazole, S-phenylbenzothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole, 6-methoxybenzothiazole, S-iodobenzothiazole, 6-iod0benzothiaz0le, 4-ethoxybenzothiazole, S-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dio);ymethylenebenz
  • a naphthothiazole nucleus e.g., a-naphthiazole, fi naphthothiazole, 5-methoxy-B-naphthothiazole, 5-ethoxy-fi-naphthothiazole, 7-methoxy-a-naphthothiazole, 8-methoxy-a-naphthothiazole, S-hydroxy-B-naphthothiazole, 7-hydroxy-u-naphthothiazole, etc.) a thianaphtheno-7,6,4,5-thiazole nucleus (e.g., '4-methoxythianaphtheno-7',6',4,S-thiazole, etc. an oxazole nucleus (e.g., 4-methyloxazole, S-methyloxazole, 4-phenyloxazole,
  • benzoxazole nucleus e.g., benzoxazole, S-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, S-methoxybenzoxazole, S-ethoxybenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, S-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.
  • benzoxazole nucleus e.g., benzoxazole, S-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, S-methoxybenzoxazole, S-ethoxybenzoxazole, 6-chlorobenzox
  • a naphthoxazole nucleus e.g., a-naphthoxazole, 5,,8-naphthoxazole, ,B-naphthoxazole, 6-hydroxy-fi-naphthoxazole, etc.
  • a selenazole nucleus e.g., 4-methylselenazole, 4-phenylselenazole, 4-(p-hydroxyphenyl) selenazole, etc.
  • a benzoselenazole nucleus e.g., benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, S-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.
  • a naphthoselenazole nucleus e.g., a-naphthoselenazole, [3,[3-naphthoselenazole, ,B-naphthoselenazole, 7-hydroxy-fi-naphthoselenazole, etc.
  • thiazoline nucleus e.g., thiazoline, 4-methylthiazoline, 4-(p-hydroxyphenyl)thiazoline, etc.
  • a quinoline nucleus e.g., quinoline, 3-methylquinoline, S-methylquinoline, 7-methylquinoline, 8-methylquin0line, 6-chloroquino1ine, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.
  • an isoquinoline nucleus e.g., isoquinoline, 3-methylisoquinoline, S-methylisoquinoline, 6-chlorois0quino1ine, 6-methoxyisoquinoline, S-hydroxyisoquinoline, etc.
  • a 3,3-dialkylindolenine nucleus e.g., 3,3-dimethylindolenine, 5-hydroxy-3,3-dimethylindolenine, 3,3,5-trimethylindolenine,
  • a pyridine nucleus e.g., pyridine, 4-methylpyridine, 6-methylpyridine, 4,6-dimethylpyridine, 4-butylpyridine, 4-decylpyridine, 4-octadecylpyridine,
  • imidazole nucleus e.g., imidazole
  • a benzimidazole nucleus e.g., benzimidazole, 5-hydroxybenzimidazole, l-alkylbenzimidazole, 1-aryl-S,6-dichlorobenzimidazole, etc.
  • a naphthimidazole nucleus e.g., l-alkyl-a-naphthimidazole, l-aryl-fi-naphthimidazole, l-alkyl-S-methoxy-a-naphthimidazole, l-alkyl-6-hydroxy-;8-naphthimidazole, etc.
  • a thiadiazole nucleus e.g., 1,2,4-thiadiazole
  • an oxadiazole nucleus e.g., 1,2,4-oxadiazole, 1,3,4-oxadiazole,
  • phenolic group or residue containing bulky quaternary nitrogen heterocyclic compounds of the invention that are especially suitable as alkalirelease mordants in photographic layers include those represented by the following general formula:
  • R and R each represent a member, such as, the hydrogen atom, a halogen atom (e.g., chlorine or bromine), an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, hexyl, dodecyl, octadecyl, benzyl, phenethyl, methoxymethyl, ethoxybutyl, isopropoxybutyl, butoxdodecyl, etc.), an aryl group (e.g., phenyl, hydroxyphenyl, tolyl, naphthyl, etc.), an alkoxy group (e.g., methoxy, ethoxy, butoxy, etc.), an aryloxy group (e.g., phenoxy, tolyloxy, naphthoxy, etc.), or a heterocyclic nu
  • any of the pyridinium salts of Formula I can be readily prepared from the corresponding pyrylium salts by reaction with the appropriate aminophenol intermediates as described hereinafter.
  • Salts of most other heterocyclic bases where the phenolic residue is in the group on the nitrogen atom have to be prepared, for example, as illustrated in the following reaction where the R group contains a phenolic residue such as previously defined IV Ills I l Han-1 and wherein d, n, B and X are as previously defined, and R represents, for example, the hydrogen atom or an alkyl group.
  • Those salts where the phenolic group is a substituent on the heterocyclic ring are conveniently prepared by a two step synthesis, for example, as illustrated in the following reaction:
  • n, B, R, R and X are as previously defined, and R represents an alkyl group.
  • any other of the heterocyclic compounds completed by Z in Formula I such as thiazoles, benzothiazoles, naphthothiazoles, oxazoles, benzoxazoles, naphthoxazoles, selenazoles, benzoselenazoles, naphthoselenazoles, thiazo lines, quinolines, indolenines, imidazoles, benzimidazoles, naphthimidizoles, thiadiazoles, oxadiazoles, triazoles, tetrazoles, etc., to give the corresponding compounds of the invention defined by Formula I above.
  • Salts of the pyrrolidone and piperidine compounds coming under Formula II above also require a two step synthesis, for example, as illustrated in the following reaction:
  • R contains the phenolic residue such as defined previously, and d, n, R and X are as previously defined. It will be understood that one or more of the carbon atoms of the heterocyclic compound can be substituted with appropriate substituents, e.g., alkyl groups such as methyl, ethyl, etc.
  • n, j, B, R and R are as previously defined, in an inert organic solvent (e.g., benzene, toluene, etc.), in approximately equimolar proportions.
  • an inert organic solvent e.g., benzene, toluene, etc.
  • the reaction is heated up to reflux temperature for a period of several minutes or more, at which time the solid product precipitates from solution.
  • the product is collected on a filter funnel and can be used, if desired, Without further purification. However, for greater purity, the precipitate can be washed with a nonsolvent such as benzene and dried.
  • the above-defined mordants of the invention function as alkali-release mordants in photographic layers.
  • they form a zwitterion with resultant internal charge compensation and at the same time 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, 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.
  • the bleaching was increased when the alkalinity of the developer was increased by the addition of sodium hydroxide.
  • the residual yellow color was discharged by subsequent acidification of the gelatin layer. This was then treated with a fixing bath of the following composition:
  • Example 1 The above results for Example 1 were made for hand coatings on cellulose acetate film support, the melts for which were prepared as follows:
  • the bleed test consisted of immersing a portion of the hand coating in stagnant, distilled water at 75 F. for two minutes and inspecting for signs of dye bleeding out of the gel layer. If no bleeding was detected, the immersion was repeated for another two minute interval. Bleachability was determined by immersion a portion of the hand coating in the developer for two 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 film processing machine.
  • the procedure for preparing the above compound was the same as Example 1 above, except that 2-amino-4- (2,4,4-trimethyl-2-pentyl)phenol was substituted for the m-aminophenol.
  • This compound was tested as a mordant in similar manner with the same dye as inExample 1 above. The results indicated that this compound is an effective alkalirelease mordant and does not retain any dye or measurable thiosulfate ion residue, after complete processing.
  • Example 3.1- 3,5 -dibromo-4-hydroxyphenyl -4,6- diphenyl-Z-picolinium iodide The above compound was prepared in accordance with the procedure of Example 1 above, except that the reactants were 2methyl4,6-diphenylpyrylium iodide and 4- amino-2,6-dibromophenol.
  • pyrylium salt intermediates include 2-methyl-4,6-di-m (and p) tolylpyrylium halides, 2,6-dimethyl-4-(3-pyridyl) pyrylium halides, 2,4-diphenyl-6-propylpyrylium halides, 2-ethyl-4,fi-di-p-tolylpyrylium halides, 2,4,6-triphenylpyrylium chloride, and the like, which are reacted with an aminophenol such as m-aminophenol, 2-amino-4-(2,4, 4-trimethyl-2-pentyl)phenol, 4-amino-2,6-dibromophenol, etc., in accordance with the processes of the above examples.
  • an aminophenol such as m-aminophenol, 2-amino-4-(2,4, 4-trimethyl-2-pentyl)phenol, 4-amino-2,6-dibromophenol, etc.
  • the photographic elements prepared with the abovedescribed 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 light-screening 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 of 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 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, ,acnylates, meth'acrylates, a-crylamide, 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. 7
  • the dyes that can be efiectively mordanted in accordance with our 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, Canadian Patent 690,133 issued July 7, 1964, having 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.
  • Other suitable acid dyes include the benzoxazolepyrazolone merocyanine dyes described in French Patent 1,359,682, issued Mar. 24, 1964, having the formula:
  • R represents an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, etc., or a ca-rboxyalkyl 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 heterocyclic nucleus of the benzoxazole series (including be'nzoxazole 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
  • 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 oarboxyl groups can be employed.
  • any filter dye containing one or more sulfo or oarboxyl groups can be employed.
  • Typical light-filtering dyes include, for example, bis(lbutyl 3 carboxymethylhexahydro 2,4,6 trioxo 5- pyrimidine)pentamethineoxonol, bis(l carboxymethyl- 3 cyclohex-ylhexahydro 2,4,6 trioxo 5 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)methineoxonol, 4 [(3 ethyl- 2(3H) benzoxazolylidine)ethylidene] 3 methyl 1- (p sulfophenyl) 2 pyrazolin 5 one monosulfonated, 4 [4 (3 ethyl 2 (3H) benzoxazolylid
  • thiazolidone sodium salt 5 (4 methoxy 3 sulfobanzal) 3 phenyl 2 phenylimino 4 thiazolidone (sodium salt), 3 phenyl 2 phenylimino 5 [3 (3 sulfobenzamido) benzal] 4 thiazolidone (sodium salt), 3 benzyl 2 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 halogensu'bstituted aliphatic acid such as mucobromic acid as described in White US. 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 naphthalene-1,5-disulfonyl chloride as described in Allen and Carroll US.
  • hardening agents as formaldehyde
  • a halogensu'bstituted aliphatic acid such as mucobromic acid as described in White US. Patent 2,080,019, issued May 11, 1937
  • a compound having a plurality of acid anhydride groups such as 7,8 di
  • dialdehyde or a sodium bisulfite derivative thereof the aldehyde groups of which are separated by 23 carbon atoms, such as [i -methyl glutaraldehyde bis-sodium bisulfite as described in Allen and Burness, Canadian Patent No. 588,451, issued Dec. 8, 1959; a bis-aziridine carboxamide such as trimethylene bis (l-aziridine earboxamide) as described in Allen and Webster US. Patent 2,950,197, issued Aug. 23, 1960; or 2,3-dihydroxydioxane as described in Jefireys US. Patent 2,870,013, issued Ian. 20, 1959.
  • 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 light-sensitive 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 light-screening layer 10 comprising gelatin, an acid substituted filter dye and the mordant of 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 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 light-sensitive layer 18 comprising gelatin, an acid substituted dye, and the mordant of Example 1 coated over layer 19, and a blue-sensitive silver halide emulsion layer 17 coated over layer 18.
  • the mordants 4 through 11 are substituted for 1-mhydroxyphenyl-2,4,6-triphenypyridinium iodide in Example l and are found to be excellent mordants which completely release acid dyes mordanted with them upon treatment with alkaline processing solutions.
  • Mordants 4 through 8 are produced by the methods described previously herein.
  • Mordants 9 through 11 are produced by alkylating the amine by methods well known in the art.
  • 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,
  • a photographic element comprising a support material having thereon a hydrophilic colloid layer containing at least one compound selected from those represented by the formula:
  • R represents a member selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group
  • R represents a member selected from the class consisting of an alkyl group, and an aryl group
  • R and R each represents a member selected from the class consisting of an alkyl group, and an aryl group
  • R and R together represent a divalent alkylene group of from 4 to 5 carbon atoms in the chain
  • X represents an acid anion
  • Z represents the nonmetallic atoms necessary to complete a 5 to 6 membered heterocyclic nucleus selected from the class consisting of a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a thionaphtheno-7
  • At least one of said R, said R and Z contains a phenolic group, and wherein said compound has a molecular weight of at least 300, said element containing light-sensitive silver halide.
  • a light-sensitive photographic element comprising a support material having thereon 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 and R each represents a member selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a Z-thienyl group, a Z-pyrryl group, a Z-indolyl group, a 3-indolyl group, a Z-furyl group, a 3-pyridyl group, and a 4-pyridyl group, and X represents an acid anion, said compound having a molecular weight of at least 300, said element containing light-sensitive silver halide.
  • 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 nondilfusible salt of a water-soluble acid dye with a compound of the formula:
  • R and R each represents a member selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, aryl group, an alkoxy group, an aryloxy group, a 2-thienyl group, a Z-pyrryl group, a 2-indolyl group, a 3-indolyl group, a 2-furyl group, a 3-pyridyl group, and a 4-pyridyl group, and X represents an acid anion, said compound having a molecular weight of at least 300'.
  • a light-sensitive photographic element comprising a support material having coated thereon at least one lightsensitive silver halide emulsion layer and having coated over said emulsion layer a hydrophilic colloid layer containing at least one substantially non-diffusible salt of a water-soluble acid dye with a compound of the formula:
  • R and R each represents a member selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a Z-thienyl group, a 2-pyrryl group, a Z-indolyl group, a 3-indolyl group, a 2-furyl group, a 3-pyridy1 group, and a 4-pyridyl group, and X represents an acid anion, said compound having a molecular weight of at least 300.
  • a photographic element of claim 2 wherein said compound is 1-(3,S-dibromo-4-hydroxyphenyl) 4,6 diium iodide.
  • a photographic element of claim 2 wherein said compound is 1-[2-hydroXy-5-(2,4,4-trimethyl-2-pentyl) phenyl] -2,4,G-triphenylpyridinium iodide.
  • a photographic element of claim 2 wherein said 15 compound is 1-(3,5-dibromo-4-hydroxyphenyl) 4,6 diphenylpicolinium iodide.
  • 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)ethylideneJ-3- methyl 1 p-sulfophenyl 2 pyrazolin-S-one monosulfonated, bis(1-butyl-3-carboxymethyl-5-barbituric acid)trimethineoxonol, 4- [4- (3-ethyl-2 (3 H) -benzoxazolylidene 2 butenylidene]-3-methyl-1-p-sulfophenyl-2-pyrazolin-5- one monosulfonated, bis(1-butyl-3-carboxymethyl-5-barbituric acid)pentamethineoxonol, bis[3-methyl-l-(p-sulfophenyl)-2-pyrazolin 5 one (4) ]met
  • 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 l p sulfophenyl-2-pyrazolin-5-one monosulfonated, bis(1-butyl-3-carboxymethyl-S-barbituric acid) trimethineoxonol, 4- [4-(3-ethyl-2 (3H) -benzoxazolylidene) Z-butenylidene]-3-methyl 1 p-sulfophenyl-2-pyrazolin- 5 one monsoulfonated, bis(1-butyl-3-carboxymethyl-5- barbituric acid)pentarnethineoxonol, bis[3-methyl-1-(psulfophenyl)-2-pyrazolin 5 one-(4) lmet
  • An element comprising a support material having thereon a hydrophilic colloid layer containing a salt of a water-soluble acid dye and at least one compound selected from those represented by the formula:
  • R represents a member selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group
  • R represents a member selected from the class consisting of an alkyl group, and an aryl group
  • R and R each represents a member selected from the class consisting of an alkyl group, and an aryl group
  • R and R together represent a divalent alkylene group of from 4 to 5 carbon atoms in the chain
  • X represents an acid anion
  • Z represents the nonmetallic atoms necessary to complete a heterocyclic nucleus having from 5- to 6-members in the beterocyclic ring, provided that at least one of the said R, said R and said Z groups contains a phenolic group, and wherein said compound has a molecular weight of at least 300.

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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
US5679505A (en) 1995-11-02 1997-10-21 Eastman Kodak Company Photographic element useful as a motion picture print film
DE69714263T2 (de) * 1997-12-02 2003-03-27 Tulalip Consultoria Comercial Sociedade Unipessoal S.A., Funchal Lichtempfindliche photographische Silberhalogenidelemente, die gelbe Filterfarbstoffe enthalten
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
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US2972535A (en) * 1957-09-03 1961-02-21 Eastman Kodak Co Quaternary salts of c-vinylpyridine polymers with compounds containing a haloacetyl group
FR1361293A (fr) * 1962-07-19 1964-05-15 Kodak Pathe Nouvelle composition de mordançage utilisable notamment en photographie

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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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